TW201808923A - Microbiocidal thiazole derivatives - Google Patents

Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as a pesticides, and especially fungicides.

Description

   Microbicidal Thiazole Derivatives   

The present invention relates to a microbicide-thiazole derivative, for example, as an active ingredient, the thiazole derivative has a microbicidal activity, particularly a fungicidal activity. The present invention also relates to the preparation of such thiazole derivatives, to agrochemical compositions containing at least one of the thiazole derivatives, and to the use of the thiazole derivatives or their compositions for controlling or preventing the use in agriculture or horticulture. The use of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms is preferably fungal infection.

WO 2010/012793 describes amine-thiazole derivatives as biocides.

According to the present invention, a compound of formula (I) is provided:

Among them, R ¹ is halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, among which C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy are optionally represented by R ⁶ Represents 1 to 3 group substitutions; R ² and R ^{4 are} independently hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or C ₃ -C ₆ cycloalkyl, wherein C _1- C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl are optionally substituted by 1 to 3 groups represented by R ⁶ ; R ³ is halogen, C ₁ -C ₆ alkyl , C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, wherein C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl are optionally R ⁶ 1 to 3 groups represented; R ⁵ is C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₃ -C ₁₀ cycloalkyl C ₁ -C ₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, aryl, heteroaryl, wherein the heteroaryl system comprises 1, 2, independently selected from nitrogen, oxygen and sulfur 5- or 6-membered aromatic monocyclic, heterocyclic group of 3 or 4 heteroatoms, wherein the heterocyclic group comprises 1, 2 or 3 heteroatoms of 4 members, independently selected from nitrogen, oxygen and sulfur, 5- or 6-membered non-aromatic monocyclic, heterocyclyl C ₁ -C ₂ alkyl, or 5- to 10-membered non-aromatic A cyclic or spiro carbon bicyclic ring system that optionally contains 1, 2, 3, 4 or 5 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and is optionally extended by C ₁ -C ₂ alkyl linkers bonded to the remainder of the molecule; wherein the C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ alkenyl and C Any of the ₂ -C ₁₀ alkynyl moieties is optionally substituted with 1 to 4 groups represented by R ⁷ or 1 group represented by R ⁸ ; or wherein the aryl, heteroaryl, and heterocyclic group Any one of the sections is optionally substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ or optionally by 1 or 2 groups represented by R ⁹ and R ¹⁰ 1 group; or wherein the cyclic or spiro carbon bicyclic ring system is optionally substituted by 1 to 3 groups represented by R ⁷ , or the cyclic carbon bicyclic ring system is optionally substituted by C ₃ -C ₆ ring Alkyl substituted to form a spiro ring moiety; R ^{6 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₆ alkoxy, and C ₃ -C ₆ cycloalkyl; R ^{7 is} independently selected from halogen, cyano group, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl , C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C _1-2 alkyl, C ₂ -C ₆ fluorenyl, C ₂ -C ₆ fluorenyloxy, C ₂ -C ₆ fluorenyloxy C ₁ -C ₆ alkyl and C ₁ -C ₄ alkoxycarbonyl; wherein when R ⁷ is In the case of C ₃ -C ₆ cycloalkyl C _1-2 alkyl, the C ₃ -C ₆ cycloalkyl moiety is optionally substituted with 1 or 2 groups independently selected from halogen and C ₁ -C ₆ alkyl R ⁸ is aryl, aryloxy, aryl C ₁ -C ₆ alkyl, heteroaryl, wherein the heteroaryl system comprises 1, 2, 3 or 4 independently selected from nitrogen, oxygen and sulfur 5 or 6 membered aromatic monocyclic, heteroaryloxy or heteroaryl C ₁ -C ₆ alkyl groups, of which aryl and heteroaryl are optionally 1 to 3 represented by R ⁹ Group or 1 group substitution represented by R ¹⁰ ; R ^{9 is} independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkane Alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy, of which C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl 1-3 radicals C ₂ -C ₆ alkynyl group optionally being substituted represented by R ^11; R ¹⁰ is selected from C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, aryl C ₁ -C ₆ alkyl, heteroaryl, wherein the heteroaryl system comprises independently selected from nitrogen, oxygen 5- or 6-membered aromatic monocyclic, 1, 2, 3, or 4 heteroatoms with sulfur, heteroaryloxy, heteroarylthio, heteroaryl C ₁ -C ₆ alkyl, heterocyclic Wherein the heterocyclyl system comprises a 4-, 5- or 6-membered non-aromatic monocyclic, heterocyclyloxy, heterocyclyl group of 1, 2 or 3 heteroatoms independently selected from nitrogen, oxygen and sulfur. Thio or heterocyclyl C ₁ -C ₆ alkyl, of which C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryl Oxy, arylthio, aryl C ₁ -C ₆ alkyl, heteroaryl, heteroaryloxy, heteroarylthio, heteroaryl C ₁ -C ₆ alkyl, heterocyclyl, hetero cycloalkyl group, a heterocyclic thio group, and heterocyclyl C ₁ -C ₆ alkyl optionally substituted with 1 to 3 groups represented by R ^11; R ¹¹ is independently selected from halogen and methyl; X is CH or N; or its salt or N- Compounds.

Surprisingly, for practical use, it has been discovered that novel compounds of formula (I) have very favorable levels of biological activity and can be used to protect plants from diseases caused by fungi.

According to a second aspect of the present invention, there is provided an agrochemical composition containing a fungicidal effective amount of a compound of formula (I) according to the present invention.

According to a third aspect of the present invention, there is provided a method for controlling or preventing the infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidal effective amount of a compound of formula (I), or comprising such a compound as an active ingredient The composition is applied to the plants, parts thereof, or their place.

According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) as a fungicide. According to this particular aspect of the invention, the use may or may not include a method of treating the human or animal body by surgery or therapy.

When substituents are represented as "optionally substituted", this means that they may or may not carry one or more of the same or different substituents, such as one, two, or three R ⁹ substituents . For example, C ₁ -C ₆ alkyl substituted with ₁ , 2 or 3 halogens may include, but is not limited to, -CH ₂ Cl, -CHCl ₂ , -CCl ₃ , -CH ₂ F, -CHF ₂ , -CF ₃ , -CH ₂ CF ₃ or -CF ₂ CH ₃ groups. As another example, a C ₁ -C ₆ alkoxy group substituted with ₁ , 2 or 3 halogens may include, but is not limited to, CH ₂ ClO-, CHCl ₂ O-, CCl ₃ O-, CH ₂ FO-, CHF _{2 O-, CF 3 O-, CF 3} CH 2 O- or CH ₃ CF ₂ O- group.

As used herein, the term "hydroxyl" or "hydroxy" refers to the -OH group.

As used herein, the term "cyano" refers to a -CN group.

As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).

As used herein, the term “C ₁ -C ₆ alkyl” refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, the hydrocarbon chain group being free of unsaturation, It has from one to six carbon atoms and it is attached to the remainder of the molecule by a single bond. The term "C ₁ -C ₁₀ alkyl" should be interpreted accordingly. Examples of C ₁ -C ₆ alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof such as isopropyl, isobutyl, two Butyl, tertiary butyl or isoamyl. "C _1- C ₆ alkylene" means a group corresponding to the definition C ₁ -C ₆ alkyl except that the group lines by two single bonds attached to the remainder of the molecule. The term "C ₁ -C ₂ alkylene" should be interpreted accordingly. Examples of C ₁ -C ₆ alkylene include, but are not limited to _{-CH 2 -, - CH 2 CH} 2 - and - (CH _{2) 3} -.

As used herein, the term "C ₂ -C ₆ alkenyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon atoms and hydrogen atoms, the hydrocarbon chain group containing at least one may be ( E ) -or ( Z ) -configured double bond with from two to six carbon atoms, which is attached to the remainder of the molecule by a single bond. The term "C ₂ -C ₁₀ alkenyl" should be interpreted accordingly. Examples of C ₂ -C ₆ alkenyl include, but are not limited to, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), and but-1-ene base.

As used herein, the term "C ₂ -C ₆ alkynyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, the hydrocarbon chain group comprising at least one triple bond, having From two to six carbon atoms, and it is attached to the remainder of the molecule by a single bond. The term "C ₂ -C ₁₀ alkynyl" should be interpreted accordingly. Examples of C ₂ -C ₆ alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.

As used herein, the term "C ₁ -C ₆ alkoxy" refers to a group having the formula -OR _a , where R _a is a C ₁ -C ₆ alkyl group as generally defined above. The term "C ₁ -C ₄ alkoxy" should be interpreted accordingly. Examples of C ₁ -C ₆ alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), propoxy, butoxy, 1-methylpropoxy And 2-methylpropoxy.

As used herein, the term "C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl" refers to having the chemical formula R _b -OR _a - group, wherein R _b is generally defined as line a C ₁ -C ₆ alkyl groups, and R _a is a C ₁ -C ₆ alkylene group as generally defined above. Examples of C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl include, but are not limited to, methoxymethyl.

As used herein, the term “C ₁ -C ₄ alkoxycarbonyl” refers to a group having the formula -C (O) OR _a , where R _a is a C _1- C ₄ alkyl group as generally defined above . Examples of C ₁ -C ₄ alkoxycarbonyl include, but are not limited to, methoxycarbonyl and ethoxycarbonyl.

As used herein, the term C ₁ -C ₆ alkylthio refers to a -SR _a group, where R _a is a C ₁ -C ₆ alkyl group as generally defined above.

As used herein, the term “C ₁ -C ₆ haloalkyl” refers to a C ₁ -C ₆ alkyl group as generally defined above, which group is replaced by one or more of the same or different halogen atoms To replace. The term "C _1- C ₄ haloalkyl" and "C _1- C ₂ haloalkyl" should be interpreted accordingly. Examples of C ₁ -C ₆ haloalkyl include, but are not limited to, trifluoromethyl.

As used herein, the term "C ₃ -C ₆ cycloalkyl" refers to a group that belongs to a monocyclic saturated ring system and contains 3 to 6 carbon atoms. The terms "C ₃ -C ₁₀ cycloalkyl" and "C ₃ -C ₈ cycloalkyl" should be interpreted accordingly and may include bridged structures (eg, norbornane). Examples of C ₃ -C ₁₀ cycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclo Hinky.

As used herein, the term "C ₃ -C ₁₀ cycloalkyl C ₁ -C ₂ alkyl" means attached to the rest of the molecule by a C ₁ -C ₂ alkyl group as defined above Part of a cycloalkyl ring. The term "C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl" is to be interpreted accordingly. Examples of C ₃ -C ₁₀ cycloalkyl C ₁ -C ₂ alkyl include, but are not limited to, cyclopropylmethyl, cyclobutylmethyl, and cyclopentylmethyl.

As used herein, the term “C ₃ -C ₁₀ cycloalkenyl” refers to a group consisting of only carbon atoms and hydrogen atoms and containing 3 to 10 carbon atoms and 1 or 2 inner ring double bonds Monocyclic non-aromatic ring system. They may include bridged structures (such as norbornene and 2,5-norbornadiene). Examples of C ₃ -C ₁₀ cycloalkenyl include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl.

As used herein, the term "C ₃ -C ₆ cycloalkoxy" refers to a group having the formula -OR _a , where R _a is a C ₃ -C ₆ cycloalkyl group as generally defined above. Examples of C ₃ -C ₆ cycloalkoxy include, but are not limited to, cyclopropoxy, cyclopentyloxy, or cyclohexyloxy.

As used herein, the term "C ₃ -C ₆ cycloalkylthio" refers to a group having the formula -SR _a , where R _a is a C ₃ -C ₆ cycloalkyl group as generally defined above. Examples of C ₃ -C ₆ cycloalkylthio include, but are not limited to, cyclopropylthio, cyclopentylthio, or cyclohexylthio.

As used herein, the term "C ₂ -C ₆ alkenyloxy" refers to a group having the formula -OR _a , where R _a is a C ₂ -C ₆ alkenyl group as generally defined above. Examples of C ₂ -C ₆ alkenyloxy include, but are not limited to, allyloxy or butenyloxy.

As used herein, the term "C ₂ -C ₆ alkynyloxy" refers to a group having the formula -OR _a , where R _a is a C ₂ -C ₆ alkynyl group as generally defined above. Examples of C ₂ -C ₆ alkynyloxy include, but are not limited to, propargyloxy or butynyloxy.

As used herein, the term "C ₂ -C ₆ fluorenyl" refers to the group R _a C (= O)-, where R _a is a C ₁ -C ₅ alkyl group or an aryl group as generally defined above group. The fluorenyl groups include, but are not limited to, ethenyl, propionyl, and benzyl.

As used herein, the term "C ₂ -C ₆ fluorenyloxy" refers to a group having the formula -OR _b , where R _b is a methyl fluorenyl or C ₂ -C ₆ fluorenyl group as generally defined above . C ₂ -C ₆ fluorenyloxy groups include, but are not limited to, ethenyloxy.

As used herein, the term "C ₂ -C ₆ acyl group C ₁ -C ₆ alkyl" refers to having the chemical formula _{R a C (= O) OR} b - group, wherein R _a line above A C ₁ -C ₅ alkyl group or an aryl group is generally defined, and wherein R _b is a C ₁ -C ₆ alkylene group as generally defined above.

As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 4-membered, 5-membered, or 6-membered non-aromatic monocyclic ring containing 1, 2, or 3 heteroatoms, wherein the The isoheteroatom is independently selected from nitrogen, oxygen, and sulfur. The heterocyclyl group may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, azetidinyl, oxetanyl, thietane, tetrahydrofuranyl, pyrrolidinyl, pyrazolyl, imidazolyl, piperidyl, Pipe base, Phenyl, dioxolanyl, dithiolanyl, and tetrahydrothiazolyl.

As used herein, the term "heterocyclyloxy" refers to a group having the formula -OR _a , where R _a is a heterocyclyl group as generally defined above. Examples of heterocyclyloxy include, but are not limited to, tetrahydrofuryloxy and Phenyloxy.

As used herein, the term "heterocyclylthio" refers to a group having the formula -SR _a , where R _a is a heterocyclyl group as generally defined above. Examples of heterocyclylthio include, but are not limited to, tetrahydrofurylthio and Phenylthio.

As used herein, the term "heterocyclyl C ₁ -C ₆ alkyl" refers to a heterocyclyl attached to the rest of the molecule through a C ₁ -C ₆ alkyl group as defined above ring. The term heterocyclyl C ₁ -C ₂ alkyl should be interpreted accordingly. Examples of heterocyclyl C ₁ -C ₆ alkyl include, but are not limited to, tetrahydrofurylmethyl or Phenylmethyl.

As used herein, the term "aryl" refers to an aromatic ring system consisting only of carbon and hydrogen atoms, which may be monocyclic-, bicyclic-, or tricyclic. Examples of such ring systems include phenyl, naphthyl, anthryl, indenyl or phenanthryl.

As used herein, the term "aryloxy" refers to a group having the formula -OR _a , where R _a is an aryl group as generally defined above. Examples of aryloxy include, but are not limited to, phenoxy and naphthyloxy.

As used herein, the term "arylthio" refers to a group having the formula -SR _a , where R _a is an aryl group as generally defined above. Examples of arylthio include, but are not limited to, phenylthio and naphthylthio.

For example, the term "aryl C ₁ -C ₆ alkyl" refers to C as defined by herein used ₁ -C ₆ alkyl group extension attached to the remainder of the molecule of the aryl ring . Examples of aryl C ₁ -C ₆ alkyl include, but are not limited to, benzyl or 2-phenylethyl.

As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing one, two, three, or four independently selected from nitrogen , Oxygen and sulfur heteroatoms. Examples of heteroaryl include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, Oxazolyl, iso Oxazolyl, triazolyl, tetrazolyl, pyr Base Group, pyrimidinyl or pyridyl.

As used herein, the term "heteroaryloxy" refers to a group having the formula -OR _a , where R _a is a heteroaryl group as generally defined above. Examples of heteroaryloxy include, but are not limited to, pyridyloxy and thienyloxy.

As used herein, the term "heteroarylthio" refers to a group having the formula -SR _a , where R _a is a heteroaryl group as generally defined above. Examples of heteroarylthio include, but are not limited to, pyridylthio and thienylthio.

As used herein, the term "heteroaryl C ₁ -C ₆ alkyl" means as defined above by C ₁ -C ₆ alkyl group attached to the heteroaryl portion of the remainder of the molecule ring. The term "heteroaryl C ₁ -C ₂ alkyl" should be interpreted accordingly.

As used herein, the term C ₁ -C ₆ alkylsulfonyl refers to a -S (O) ₂ R _a group, where R _a is a C ₁ -C ₆ alkyl group as generally defined above. .

As used herein, the term C ₁ -C ₆ alkylcarbonyloxy refers to a -OC (= O) R _a group, where R _a is a C ₁ -C ₆ alkyl group as generally defined above. .

As used herein, = O represents a pendant oxy group, such as seen in a carbonyl (-C (= O)-) group.

As used herein, a "cyclic carbon bicyclic ring" is a non-aromatic bicyclic ring system that contains two rings fused together, that is, sharing two carbon atoms.

As used herein, a "spiro-carbon bicyclic ring" is a non-aromatic bicyclic ring system that contains two rings linked together on one carbon atom, that is, sharing one carbon atom.

The presence of one or more carbon atoms that may be asymmetric in the compound of formula (I) indicates that the compounds can occur as optical isomers, that is, as mirror images or non-image mirrors. Atropisomers may also exist as a result of restricted rotations around single bonds. The purpose of Chemical Formula (I) is to include all those possible isomeric forms as well as mixtures thereof. The invention includes all those possible isomeric forms and mixtures thereof directed to compounds of formula (I). Likewise, formula (I) is intended to include all possible tautomers. The invention includes all possible tautomeric forms for compounds of formula (I).

In each case, the compounds of formula (I) according to the present invention are free, oxidized (e.g. N-oxide) or salt (e.g. agronomically usable salt forms).

An oxidized form of an N-oxide-based tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. For example, A. Albini and S. Pietra published in 1991 at the Boca Raton CRC Press entitled "Heterocyclic N-oxides" (" Heterocyclic N-oxides ").

Regarding compounds of formula (I), the following list provides the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ and X Definitions, including better definitions. For any of these substituents, any definitions given below may be combined with any definitions of any other substituents given below or elsewhere in this document.

R ¹ Department of halo, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, wherein C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy group optionally represented by R ⁶ 1 to 3 groups are substituted. R ¹ may be halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, where C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy are optionally represented by R ⁶ 1 to 3 groups. Preferably, R ¹ is halogen, cyano, methyl, trifluoromethyl, methoxy or trifluoromethoxy. More preferably, R ¹ is halogen or cyano, even more preferably halogen, and even more preferably fluorine.

R ² is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, of which C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C _{The 3-} C ₆ cycloalkyl group is optionally substituted with 1 to 3 groups represented by R ⁶ . Preferably, R ² is hydrogen or C ₁ -C ₆ alkoxy (including C ₁ -C ₄ alkoxy), more preferably hydrogen or methoxy, and even more preferably hydrogen.

R ³ is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, of which C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C _{The 3-} C ₆ cycloalkyl group is optionally substituted with 1 to 3 groups represented by R ⁶ . Preferably, R ³ is halogen or C ₁ -C ₆ alkyl (including C ₁ -C ₄ alkyl), more preferably halogen (specifically chlorine or bromine) or methyl, even more preferably Is bromine or methyl, and still more preferably methyl.

R ⁴ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, of which C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C _{The 3-} C ₆ cycloalkyl group is optionally substituted with 1 to 3 groups represented by R ⁶ . Preferably, R ⁴ is hydrogen or C ₁ -C ₆ alkoxy (including C ₁ -C ₄ alkoxy); more preferred is hydrogen or methoxy, and even more preferred is hydrogen.

Department of R ⁵ C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkyl C ₁ -C ₂ alkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ alkynyl, aryl, heteroaryl, wherein the heteroaryl system comprises 5 members or 6 members of 1, 2, 3 or 4 heteroatoms independently selected from nitrogen, oxygen and sulfur Membered aromatic monocyclic, heterocyclic group, wherein the heterocyclic group comprises 1, 2, or 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 4-, 5-, or 6-membered non-aromatic monocyclic ring, Heterocyclyl C ₁ -C ₂ alkyl, or 5 to 10 members (preferably, 7 to 10 members) non-aromatic cyclic or spiro carbon bicyclic ring system, the carbon bicyclic ring ring system optionally includes separately 1, 2, 3, 4, or 5 heteroatoms selected from nitrogen, oxygen, and sulfur, and optionally bonded to the remainder of the molecule through a C ₁ -C ₂ alkyl linker; wherein the C _1- Any of C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ alkenyl, and C ₂ -C ₁₀ alkynyl moieties are optionally represented by R ⁷ 1 to 4 groups or 1 group represented by R ⁸ ; or wherein any one of the aryl, heteroaryl, and heterocyclic moiety is optionally represented by R ⁹ 1 to 3 groups or 1 group represented by R ¹⁰ , or optionally 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; or wherein the ring The cyclic or spiro carbon bicyclic ring is optionally substituted with 1 to 3 groups represented by R ⁷ , or the cyclic carbon bicyclic ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spiro ring moiety.

Preferably, R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, phenyl, heteroaryl, wherein the heteroaryl system comprises 1, 2, 3 or 4 heteroatoms independently selected from nitrogen, oxygen and sulfur 5-membered or 6-membered aromatic monocyclic, heterocyclic group, wherein the heterocyclic group system contains 1, 2, or 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur of 4-, 5-, or 6-membered non- monocyclic aromatic, heterocyclyl C ₁ -C ₂ alkyl group, or a 5-10 spiro non-aromatic cyclic or bicyclic carbon ring system, the bicyclic ring system optionally comprises carbon independently selected from nitrogen, oxygen and sulfur 1, 2 or 3 heteroatoms, and optionally bonded to the remainder of the molecule through a C ₁ -C ₂ alkyl linker; wherein the C ₁ -C ₆ alkyl, C ₃ -C ₆ ring Any of the alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, and C ₂ -C ₆ alkynyl moieties are optionally represented by 1 to 4 groups represented by R ⁷ or R ⁸ 1 group substitution; or wherein any one of the phenyl, heteroaryl, and heterocyclic moiety is optionally represented by 1 to 3 groups represented by R ⁹ or R ¹⁰ 1 group, or optionally 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; or wherein the cyclic or spiro carbon bicyclic ring is optionally substituted by R ⁷ The 1 to 3 groups represented are substituted, or the cyclic carbon bicyclic ring system is optionally substituted with a C ₃ -C ₆ cycloalkyl group to form a spiro ring moiety.

More preferably, R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₅ cycloalkyl C _1-2 alkyl, C ₂ -C ₆ alkynyl, benzene A heterocyclic group, wherein the heterocyclic group contains a 4-membered or 6-membered non-aromatic monocyclic ring of 1 oxygen atom, a heterocyclyl C ₁ alkyl group, or a 5- to 9-membered non-aromatic cyclic or spiro ring A carbon bicyclic ring system, which optionally contains 1 oxygen atom, and optionally bonded to the remainder of the molecule via a methylene (-CH _2- ) linker; wherein the C ₁ -C ₆ alkyl group Any of the C ₃ -C ₆ cycloalkyl and C ₂ -C ₆ alkynyl moieties are optionally substituted with 1 to 4 groups represented by R ⁷ or 1 group represented by R ⁸ ; wherein Any one of the phenyl or heterocyclyl moiety is optionally substituted with 1 or 2 groups represented by R ⁹ or 1 group represented by R ¹⁰ or optionally by 1 or 2 groups represented by R ⁹ And 1 group represented by R ¹⁰ ; and wherein the cyclic or spiro carbon bicyclic ring is optionally substituted by 1 or 2 groups represented by R ⁷ or the cyclic carbon bicyclic ring system is optionally substituted by C _{4- C5} cycloalkyl is substituted to form a spiro ring moiety.

Even more preferably, R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl or C ₂ -C ₆ alkynyl wherein the C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl and the alkyl moiety is optionally any indicated R ⁷ 1 to 4 groups represented by R ^8, or 1 group substitution, wherein R ^{7 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy C _1- C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C _1-2 alkyl, and C ₁ -C ₃ alkoxycarbonyl, where R ⁸ is Optionally a phenyl, benzyl or iso group substituted with 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ Azole, and wherein R ⁹ is a halogen and R ¹⁰ is optionally a phenyl group substituted with 1 to 3 groups of halogen represented by R ¹¹ .

Still more preferably, R ⁵ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl , Which is optionally substituted by a group represented by R ⁷ , wherein R ⁷ is methyl, hydroxyl, cyano, trifluoromethyl, methoxymethyl, C ₃ -C ₆ cycloalkyl, ethoxy Carbonyl, ethynyloxymethyl or 2,2-dichlorocyclopropyl; or optionally substituted by 2 groups represented by R ⁷ , where each R ^{7 is} independently methyl, cyano or Cyclopropyl; or optionally substituted by 3 groups represented by R ⁷ , where each R ^{7 is} independently methyl, bromine, chlorine, fluorine, or butoxy; or optionally by 4 represented by R ⁷ Each group is substituted, wherein each R ⁷ is methyl, or optionally substituted by 1 group represented by R ⁸ , wherein R ⁸ is optionally substituted by 1 to 3 groups represented by R ⁹ or R ¹⁰ 1 group substituted phenyl, benzyl or iso Azole, and wherein R ⁹ is halogen and R ¹⁰ is optionally substituted by 1 to 3 groups represented by R ¹¹ as halogen; or R ⁵ is phenyl, pyridylmethyl (including 2-pyridine) Methyl, 3-pyridylmethyl and 4-pyridylmethyl), oxetanyl (including oxetan-2-yl, oxetan-3-yl), tetrahydrofuranyl (Tetrahydrofuran-2-yl, tetrahydrofuran-3-yl) or tetrahydropiperanyl (tetrahydropiperan-2-yl, tetrahydropiperan-3-yl, tetrahydropiperan-4-yl), each of which Optionally substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ , wherein R ^{9 is} independently selected from halogen and C ₁ -C ₄ alkyl, and R ^{10 is} selected from phenyl, benzyl, or C ₆ -C ₈ cycloalkoxy, each of which is optionally 1 to 3 represented by R ¹¹ Or R ⁵ is selected from the following cyclic or spiro ring systems:

Each is optionally substituted by 1 to 3 groups represented by R ⁷ which are independently selected from C ₁ -C ₄ alkyl and C ₂ -C ₄ amidinooxy C ₁ -C ₄ alkyl : Still more preferably, R ⁵ is optionally a C ₁ -C ₄ alkyl group substituted with ₁ group represented by R ⁷ selected from C ₃ -C ₆ cycloalkyl; or R ⁵ is selected from The following ring or spiral ring systems:

Each is optionally substituted by 1 to 3 groups represented by R ⁷ , which are independently selected from C ₁ -C ₄ alkyl, specifically methyl.

In a particular preferred embodiment of the present invention, R ⁵ lines (3,4-difluorophenyl) methyl, (2,4,5-trifluorophenyl) methyl, (2-chloro - 4,5-difluorophenyl) methyl, (2-bromo-4,5-difluorophenyl) methyl, 1-cyclohexylethyl, 1-phenylethyl, 1- (3-phenyl different Azol-5-yl) ethyl, 1- [3- (2-iodophenyl) iso Azol-5-yl] ethyl, [2-methyl-1- (trifluoromethyl) propyl], [1- (hydroxymethyl) -2,2-dimethyl-propyl], (1 -Benzyl-2,2-dimethyl-propyl), (1-isopropyl-2-methyl-but-3-ynyl), [1- (1-cyanoethyl) -2- Methyl-propyl], [3-methyl-1- (1-methyl-2-phenyl-ethyl) butyl], (1-cyclohexylcyclopropyl), (3-isobutoxy -2,2-dimethyl-cyclobutyl), spiro [3.3] heptane-7-yl], [(7R) -spiro [3.3] heptane-7-yl], spiro [3.4] octane- 3-yl, spiro [3.4] octane-2-yl, [3- (ethoxymethyl) -8-oxaspiro [3.4] octane-1-yl], spiro [3.5] nonane- 2-yl, [(1R, 5S, 6R) -6-bicyclo [3.2.0] heptyl], [(1S, 5R, 7R) -5-methyl-7-bicyclo [3.2.0] heptane Group], 6,6-dimethyl-7-bicyclo [3.2.0] heptyl], [(1S, 5R, 7S) -6,6-dimethyl-7-bicyclo [3.2.0] heptane Alkyl], [(1S, 5S) -6,6-dimethyl-7-bicyclo [3.2.0] hept-3-enyl], (6,6-dimethyl-4-oxabicyclo [ 3.2.0] heptane-7-yl), spiro [4-oxabicyclo [3.2.0] heptane-6,1'-cyclobutane] -7-yl, spiro [4-oxabicyclo [3.2 .0] heptane-6,1'-cyclopentane] -7-yl, [(1S, 6R, 8R) -6-methyl-8-bicyclo [4.2.0] octyl], (7, 7-dimethyl-5-oxabicyclo [4.2.0] octane-8-yl ), (1-benzylcyclohexyl), (3,3,5,5-tetramethylcyclohexyl), (6-methyl-2-bicyclo [4.2.0] octyl), [(3S) -2- (2,4-dichlorophenyl) oxetan-3-yl], (4-benzyl-2,6-dimethyl-tetrahydropiperan-4-yl), [4 -(4,4-dimethylcyclohexyloxy) -2-fluoro-phenyl], [4- (cyclooctyloxy) -2-fluoro-phenyl], [4- (4-chlorobenzene (Oxy) phenyl], 2,2-dimethylpropyl, (1-methylcyclopropyl) methyl, (1-methylcyclopentyl) methyl, (4-methyltetrahydropiperan -4-yl) methyl, (3-methoxy-2,2-dimethyl-propyl), (1-methylcyclobutyl) methyl, (1-cyclopropylcyclopropyl), (1-cyano-1-cyclopropyl-ethyl), (1-ethoxycarbonylcyclopropyl) methyl, [1- (cyclopropylmethyl) cyclopropyl] methyl, (3- Methyloxetane-3-yl) methyl, (1-methoxycyclopentyl) methyl, 1- (2-pyridyl) ethyl, spiro [2.2] pentane-5-yl, [1- (methoxymethyl) cyclopropyl] methyl, 6-oxaspiro [2.5] octane-2-ylmethyl, [1- (trifluoromethyl) cyclopropyl] methyl and [1- (methoxymethyl) cyclopentyl] methyl.

In an even more preferred embodiment, R ⁵ is (3,4-difluorophenyl) methyl, (2,4,5-trifluorophenyl) methyl, (2-chloro-4,5- Difluorophenyl) methyl, (2-bromo-4,5-difluorophenyl) methyl, 1-cyclohexylethyl, 1-phenylethyl, 1- (3-phenyliso Azol-5-yl) ethyl, 1- [3- (2-iodophenyl) iso Azol-5-yl] ethyl, [2-methyl-1- (trifluoromethyl) propyl], [1- (hydroxymethyl) -2,2-dimethyl-propyl], (1 -Benzyl-2,2-dimethyl-propyl), (1-isopropyl-2-methyl-but-3-ynyl), [1- (1-cyanoethyl) -2- Methyl-propyl], [3-methyl-1- (1-methyl-2-phenyl-ethyl) butyl], (1-cyclohexylcyclopropyl), (3-isobutoxy -2,2-dimethyl-cyclobutyl), spiro [3.3] heptane-7-yl], [(7R) -spiro [3.3] heptane-7-yl], spiro [3.4] octane- 3-yl, spiro [3.4] octane-2-yl, [3- (ethoxymethyl) -8-oxaspiro [3.4] octane-1-yl], spiro [3.5] nonane- 2-yl, [(1R, 5S, 6R) -6-bicyclo [3.2.0] heptyl], [(1S, 5R, 7R) -5-methyl-7-bicyclo [3.2.0] heptane Group], 6,6-dimethyl-7-bicyclo [3.2.0] heptyl], [(1S, 5R, 7S) -6,6-dimethyl-7-bicyclo [3.2.0] heptane Alkyl], [(1S, 5S) -6,6-dimethyl-7-bicyclo [3.2.0] hept-3-enyl], (6,6-dimethyl-4-oxabicyclo [ 3.2.0] heptane-7-yl), spiro [4-oxabicyclo [3.2.0] heptane-6,1'-cyclobutane] -7-yl, spiro [4-oxabicyclo [3.2 .0] heptane-6,1'-cyclopentane] -7-yl, [(1S, 6R, 8R) -6-methyl-8-bicyclo [4.2.0] octyl], (7, 7-dimethyl-5-oxabicyclo [4.2.0] octane-8-yl ), (1-benzylcyclohexyl), (3,3,5,5-tetramethylcyclohexyl), (6-methyl-2-bicyclo [4.2.0] octyl), [(3S) -2- (2,4-dichlorophenyl) oxetan-3-yl], (4-benzyl-2,6-dimethyl-tetrahydropiperan-4-yl), [4 -(4,4-dimethylcyclohexyloxy) -2-fluoro-phenyl], [4- (cyclooctyloxy) -2-fluoro-phenyl], [4- (4-chlorobenzene (Oxy) phenyl], 2,2-dimethylpropyl, (1-methylcyclopropyl) methyl, (1-methylcyclopentyl) methyl, (4-methyltetrahydropiperan -4-yl) methyl, (3-methoxy-2,2-dimethyl-propyl), (1-methylcyclobutyl) methyl, (1-cyclopropylcyclopropyl), (1-cyano-1-cyclopropyl-ethyl), (1-ethoxycarbonylcyclopropyl) methyl, [1- (cyclopropylmethyl) cyclopropyl] methyl, (3- Methyloxetane-3-yl) methyl, 1- (2-pyridyl) ethyl, spiro [2.2] pentane-5-yl, [1- (trifluoromethyl) cyclopropyl] Methyl and [1- (methoxymethyl) cyclopentyl] methyl.

In still more preferred embodiments, R ⁵ is 1-cyclohexylethyl, 1-phenylethyl, 1- (3-phenyliso Azole-5-yl) ethyl, spiro [3.3] heptane-7-yl], spiro [3.4] octane-3-yl, spiro [3.4] octane-2-yl, spiro [3.5] nonane- 2-yl, [3- (ethoxymethyl) -8-oxaspiro [3.4] octane-1-yl], 6,6-dimethyl-7-bicyclo [3.2.0] heptane Group], (6,6-dimethyl-4-oxabicyclo [3.2.0] heptane-7-yl), spiro [4-oxabicyclo [3.2.0] heptane-6,1'- Cyclobutane] -7-yl, spiro [4-oxabicyclo [3.2.0] heptane-6,1'-cyclopentane] -7-yl, (6-methyl-2-bicyclo [4.2. 0] octyl) and spiro [2.2] pentane-5-yl.

R ^{6 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₆ alkoxy, and C ₃ -C ₆ cycloalkyl. Preferably, R ^{6 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₄ alkoxy, and C ₃ -C ₆ cycloalkyl.

R ^{7 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C _1-2 alkyl, C ₂ -C ₆ fluorenyl, C ₂ -C ₆ fluorenyloxy, C ₂ -C _6- Amidyloxy C ₁ -C ₆ alkyl and C ₁ -C ₄ alkoxycarbonyl.

Preferably, R ^{7 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C _1-2 alkyl, and C _1- C ₄ alkoxycarbonyl; wherein the C ₃ -C ₆ ring The alkyl moiety is optionally substituted with 1 or 2 groups selected from halogen and C ₁ -C ₆ alkyl.

More preferably, R ^{7 is} independently selected from chlorine, bromine, fluorine, cyano, hydroxy, methyl, trifluoromethyl, methoxy, butoxy, methoxymethyl, cyclopropyl, cyclo Hexyl, cyclooctyl, cyclopropylmethyl, ethenyloxymethyl and ethoxycarbonyl; wherein cyclopropyl is optionally substituted with 2 chloro groups.

R ⁸ is aryl, aryloxy, aryl C ₁ -C ₆ alkyl, heteroaryl, wherein the heteroaryl system comprises 1, 2, 3 or 4 independently selected from nitrogen, oxygen and sulfur 5- or 6-membered heteroaromatic monocyclic, heteroaryloxy or heteroaryl C ₁ -C ₆ alkyl, of which aryl and heteroaryl are optionally 1 to 3 groups represented by R ⁹ Or 1 group represented by R ¹⁰ .

Preferably, R ⁸ is a phenyl, benzyl or iso group substituted with 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ as appropriate. Azole. More preferably, R ⁸ is phenyl, benzyl or iso Azole Yl optionally substituted with a group represented by R ^10.

R ^{9 is} independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy, of which C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkane Thiol, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy, optionally 1 to 3 represented by R ¹¹ Groups are substituted. Preferably, R ⁹ is independently selected from halogen, cyano, hydroxy and C ₁ -C ₄ alkyl. More preferably, R ^{9 is} independently selected from chlorine, bromine, fluorine and methyl.

R ^{10 is} selected from C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, aryl C _1- C ₆ alkyl, heteroaryl, wherein the heteroaryl system comprises 1, 2, 3, or 4 heteroatoms of 5 or 6 membered aromatic monocyclic, hetero Aryloxy, heteroarylthio, heteroaryl C ₁ -C ₆ alkyl, heterocyclyl, wherein the heterocyclyl system comprises 1, 2 or 3 hetero atoms independently selected from nitrogen, oxygen and sulfur 4-, 5-, or 6-membered non-aromatic monocyclic, heterocyclyloxy, heterocyclylthio, and heterocyclyl C ₁ -C ₆ alkyl, of which C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkyl group, aryl group, aryloxy group, arylthio, aryl-C ₁ -C ₆ alkyl, heteroaryl, heteroaryl Oxy, heteroarylthio, heteroaryl C ₁ -C ₆ alkyl, heterocyclyl, heterocyclyloxy, heterocyclylthio, and heterocyclyl C ₁ -C ₆ alkyl are optionally R 1 to 3 groups represented by ¹¹ ; preferably, R ^{10 is} selected from phenyl, benzyl and C ₆ -C ₈ cycloalkoxy, each of which is optionally 1 to 3 represented by R ¹¹ Groups are substituted. More preferably, R ¹⁰ is a phenyl group, which is optionally substituted with one R ¹¹ .

R ^{11 is} independently selected from halogen and methyl.

X is CH or N. In one embodiment of the present invention, X is CH. In another embodiment of the present invention, X is N.

According to the present invention, it is preferred that: R ¹ is halogen or cyano; R ² is hydrogen or C ₁ -C ₄ alkoxy; R ³ is halogen or C ₁ -C ₆ alkyl; R ⁴ is hydrogen; R ⁵ series C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl , C ₂ -C ₆ alkynyl, phenyl, heteroaryl, wherein the heteroaryl system comprises 5 or 6 members of 1, 2, 3 or 4 heteroatoms independently selected from nitrogen, oxygen and sulfur Aromatic monocyclic, heterocyclyl, wherein the heterocyclyl system comprises a 4-, 5-, or 6-membered non-aromatic monocyclic, hetero Cyclo C _1- C ₂ alkyl or 5- to 10-membered non-aromatic cyclic or spiro carbon bicyclic ring system, the carbon bicyclic ring system optionally contains 1, 2 or 3 independently selected from nitrogen, oxygen and sulfur Heteroatom, and optionally bonded to the remainder of the molecule via a C _1- C ₂ alkyl linker; wherein the C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C Any one of the _6- cycloalkenyl, C ₂ -C ₆ alkenyl and C ₂ -C ₆ alkynyl moieties is optionally substituted with 1 to 4 groups represented by R ⁷ or 1 group represented by R ⁸ ; Or its 1 to 3 groups or R 1 radicals represented by any one of optionally said phenyl, heteroaryl and heterocyclyl portions are indicated ¹⁰ substituted R ^9, or optionally R ⁹ is represented by 1 or 2 groups and 1 group represented by R ¹⁰ ; and wherein the cyclic or spiro carbon bicyclic ring system is optionally substituted with 1 to 3 groups represented by R ⁷ or the cyclic group The carbobicyclic system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spiro ring moiety; and R ^{7 is} independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl , C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl , C ₂ -C ₄ fluorenyloxy C ₁ -C ₄ alkyl and C _1- C ₄ alkoxycarbonyl, wherein C ₃ -C ₆ cycloalkyl C _1-2 alkyl C ₃ -C ₆ ring The alkyl moiety is optionally substituted by 1 or 2 groups selected from halogen and C ₁ -C ₆ alkyl; R ⁸ is optionally 1 to 3 groups represented by R ⁹ or 1 represented by R ¹⁰ Phenyl, benzyl or iso Azole; R ^{9 is} independently selected from halogen and C ₁ -C ₄ alkyl; R ¹⁰ is phenyl, benzyl or C ₆ -C ₈ cycloalkane optionally substituted with 1 to 3 groups represented by R ¹¹ R ¹¹ is halogen; and X is CH.

More preferably, R ¹ is halogen; R ² is hydrogen or methoxy; R ³ is bromine or methyl; R ⁴ is hydrogen; R ⁵ is C ₁ -C ₆ alkyl; C ₃ -C ₆ ring Alkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, phenyl, heteroaryl Wherein the heteroaryl system comprises a 5-, or 6-membered aromatic monocyclic, heterocyclic group of 1, 2, or 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, wherein the heterocyclic system comprises individually 4-, 5- or 6-membered non-aromatic monocyclic, 1, 2 or 3 heteroatoms selected from nitrogen, oxygen and sulfur, heterocyclic C _1- C ₂ alkyl or 5- to 10-membered non-aromatic spiro cyclic or bicyclic carbon ring system, the bicyclic ring system optionally comprises carbon independently selected from nitrogen, oxygen and sulfur, 2 or 3 heteroatoms, and optionally by C _1- C ₂ alkylene linker bond To the remainder of the molecule; wherein the C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, and C ₂ -C ₆ Any of the alkynyl moieties is optionally substituted with 1 to 4 groups represented by R ⁷ or 1 group represented by R ⁸ ; wherein any of the phenyl, heteroaryl, and heterocyclyl moieties One is optionally substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ or optionally by 1 or 2 groups represented by R ⁹ and 1 represented by R ¹⁰ groups; and wherein the cyclic or spiro ring carbon double ring optionally with 1 to 3 groups represented by R ⁷ are substituted, the cyclic carbon or bicyclic ring system optionally substituted with C ₃ -C ₆ cycloalkyl group in Forms a spiro ring moiety; and R ^{7 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkane Oxyl C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl, C ₂ -C ₄ amidinooxy C ₁ -C ₄ alkyl group and a C _1- C ₄ alkoxycarbonyl group, wherein the C ₃ -C ₆ cycloalkyl C _1-2 alkyl C ₃ -C ₆ cycloalkyl moiety is optionally selected from halogen and C ₁ -C ₆ alkyl 1 or 2 groups of a radical; R ⁸ is optionally a phenyl, benzyl or iso group substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ Azole; R ^{9 is} independently selected from halogen and C ₁ -C ₄ alkyl; R ¹⁰ is phenyl, benzyl or C ₆ -C ₈ cycloalkane optionally substituted with 1 to 3 groups represented by R ¹¹ R ¹¹ is halogen; and X is CH.

Even more preferably, R ¹ is fluorine; R ² is hydrogen; R ³ is bromine or methyl; R ⁴ is hydrogen; R ⁵ is optionally R ⁷ selected from C ₃ -C ₆ cycloalkyl C ₁ -C ₆ alkyl substituted by ₁ group, or a cyclic or spiro ring system selected from:

Each is optionally substituted by 1 to 3 groups represented by R ⁷ , which are independently selected from C ₁ -C ₄ alkyl.

Still more preferably, R ¹ is fluorine; R ² is hydrogen; R ³ is bromine or methyl; R ⁴ is hydrogen; R ⁵ is optionally R selected from cyclopropyl, cyclopentyl or cyclohexyl 1 group substituted C _1-4 alkyl represented by ⁷ , or a cyclic or spiro ring system selected from:

Each is optionally substituted with 1 to 3 groups represented by R ⁷ independently selected from methyl.

In another preferred embodiment, R ¹ is fluorine; R ² is hydrogen; R ³ is bromine or methyl; R ⁴ is hydrogen; R ⁵ is C ₁ -optionally substituted with ₁ cyclohexyl group C ₄ alkyl; or a cyclic or spiro ring system selected from:

Each is optionally substituted by 1 or 2 groups represented by R ⁷ , wherein R ⁷ is methyl.

Preferably, the compound according to formula (I) is selected from:

5-bromo-N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline) thiazole-4-carboxamide;

N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxamide;

5-bromo-2- (3,5-difluoroaniline) -N-spiro [3.3] heptane-7-yl-thiazole-4-carboxamide;

2- (3,5-difluoroaniline) -5-methyl-N-spiro [3.3] heptane-7-yl-thiazole-4-carboxamide;

5-bromo-2- (3,5-difluoroaniline) -N-spiro [3.4] octan-3-yl-thiazole-4-carboxamide;

2- (3,5-difluoroaniline) -5-methyl-N-spiro [3.4] octane-3-yl-thiazole-4-carboxamide;

5-bromo-2- (3,5-difluoroaniline) -N- (6,6-dimethyl-7-bicyclo [3.2.0] heptyl) thiazole-4-carboxamide;

2- (3,5-difluoroaniline) -N- (6,6-dimethyl-7-bicyclo [3.2.0] heptyl) -5-methyl-thiazole-4-carboxamide;

5-bromo-2- (3,5-difluoroaniline) -N- (6-methyl-2-bicyclo [4.2.0] octyl) thiazole-4-carboxamide;

2- (3,5-difluoroaniline) -5-methyl-N- (6-methyl-2-bicyclo [4.2.0] octyl) thiazole-4-carboxamide;

2-[(2,6-difluoro-4-pyridyl) amino] -5-methyl-N-spiro [3.4] octane-3-yl-thiazole-4-carboxamide;

5-bromo-2-[(2,6-difluoro-4-pyridyl) amino] -N-spiro [3.4] octane-3-yl-thiazole-4-carboxamide;

5-chloro-2-[(2,6-difluoro-4-pyridyl) amino] -N-spiro [3.4] octane-3-yl-thiazole-4-carboxamide;

2-[(2,6-difluoro-4-pyridyl) amino] -5-methyl-N-spiro [2.2] pentane-2-yl-thiazole-4-carboxamide;

2- (3,5-difluoroaniline) -5-methyl-N-spiro [2.2] pentane-2-yl-thiazole-4-carboxamide; and

5-chloro-2-[(2,6-difluoro-4-pyridyl) amino] -N-spiro [2.2] pentane-2-yl-thiazole-4-carboxamide.

The invention also relates to compounds of formula I-1:

Wherein ^{R 1, R 2, R 3} , R 4 and R ⁵ have the formula I as defined above. Preferred definitions of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined in formula (I).

The invention also relates to compounds of formula I-2:

Wherein R ² , R ³ , R ⁴ , R ⁵ and X have the definitions as described in Chemical Formula I. Preferred definitions of R ² , R ³ , R ⁴ , R ⁵ and X are as defined in formula (I).

The invention also relates to compounds of formula I-3:

Wherein R ¹ , R ³ , R ⁴ , R ⁵ and X have the definitions as described in Chemical Formula (I). Preferred definitions of R ¹ , R ³ , R ⁴ , R ⁵ and X are as defined in formula (I).

The invention also relates to compounds of formula I-4:

Wherein R ¹ , R ² , R ⁴ , R ⁵ and X have the definitions as described in Chemical Formula (I). Preferred definitions of R ¹ , R ² , R ⁴ , R ⁵ and X are as defined in formula (I).

The invention also relates to compounds of formula I-5:

Wherein R ¹ , R ² , R ³ , R ⁵ and X have the definitions as described in Chemical Formula (I). Preferred definitions of R ¹ , R ² , R ³ , R ⁵ and X are as defined in formula (I).

Another preferred embodiment of the present invention is embodiments EI.a to EI.bk, which are defined as one chemical formula selected from the group consisting of the chemical formulas (Ia) to (I.bk) described below. The compound of the formula (I) represented, wherein in the formulas (Ia) to (I.bk), the meanings of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the above-mentioned preferred Meaning or one of the meanings 1 to 80 corresponding to those given in Table 1.

For example, embodiment EI.a is represented by a compound of formula (Ia)

And the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have one of the meanings as defined above or one of the meanings 1 to 80 given in Table 1.

Embodiments EI.b to EI.bk are defined accordingly and the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the meanings as defined above or the meanings given in Table 1 corresponding to 1 to 80 one.

The compounds of the present invention can be prepared as shown in the following scheme, wherein (unless otherwise stated) the definition of each variable is as defined above for the compound of formula (I).

The compound of formula (I) according to the present invention (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined in formula (I)) can be obtained by: Compounds of formula (II) (wherein R ¹ , R ² and X are as defined in formula (I)) are heated with heat or with the aid of a base or under transition metal-catalyzed Buchwald-Hartwig amination. Compounds of formula (III) (wherein R ³ , R ⁴ and R ⁵ are as defined in formula (I) and R ¹² is a halogen, preferably bromine) are converted. This is shown in Scheme 1 below.

Compounds of formula (III) (wherein R ³ , R ⁴ and R ⁵ are as defined in formula (I), and R ¹² is halogen, preferably bromine) can be obtained by:醯 Chlorine or directly using a peptide coupling agent, a compound of formula (IV) (where R ³ is as defined in formula (I) and R ⁹ is a halogen, preferably bromine) and a compound of formula (V) Compounds (wherein R ⁴ and R ⁵ are as defined in formula (I)) are converted. This is shown in Scheme 2 below.

Compounds of formula (IV) (wherein R ³ is as defined in formula (I) and R ¹² is halogen, preferably bromine) can be converted to a compound of formula (VI) (wherein R ³ is as R ¹² is a halogen, preferably bromine, and R ¹³ is a C ₁ -C ₆ alkyl group), as defined in formula (I). This is shown in Scheme 3 below.

Alternatively, compounds of formula (I) having the (wherein ^{R 1, R 2, R 3} , R 4, R 5 and X are as defined lines of formula (I)) can be obtained by the following manner: by Intermediate醯 Chlorine or directly with a peptide coupling agent, a compound of formula (VII) (where R ¹ , R ² , R ³ and X are as defined in formula (I)) and a compound of formula (V) (where R ⁴ and R ⁵ are transformed as defined in formula (I)). This is shown in Scheme 4 below.

Compounds of formula (VII) (wherein R ¹ , R ² , R ³ and X are as defined in formula (I)) can be converted with a base to compounds of formula (VIII) (where R ¹ , R ² , R ³ And X are as defined in formula (I), and R ¹³ is C ₁ -C ₆ alkyl). This is shown in Scheme 5 below.

Compounds of formula (VIII) (wherein R ¹ , R ² , R ³ and X are as defined in formula (I) and R ¹³ is C ₁ -C ₆ alkyl) can be obtained by: Compounds of formula (II) (wherein R ¹ , R ² and X are as defined in formula (I)) are heated with heat or with the aid of a base or under the conditions of transition metal-catalyzed Buchwald-Hartwig amination. Compounds of formula (VI) (wherein R ³ is as defined in formula (I), R ¹² is halogen, preferably bromine, and R ¹³ is C ₁ -C ₆ alkyl) are converted. This is shown in Scheme 6 below.

Alternatively, the compound of formula (VIII) (wherein R ¹ , R ² , R ³ and X are as defined in formula (I), and R ¹³ is C ₁ -C ₆ alkyl) can be obtained as follows Obtained: Under transition metal-catalyzed Buchwald-Hartwig amination conditions, a compound of formula (IX) (wherein R ¹ and X are as defined in formula (I), and R ¹² is a halogen, preferably bromine Or iodine) with a compound of formula (X) (wherein R ² and R ³ are as defined in formula (I) and R ¹³ is C ₁ -C ₆ alkyl). This is shown in Scheme 7 below.

Alternatively, the compound of formula (I) according to the present invention (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined in formula (I)) can be obtained as follows Obtained: Under transition metal-catalyzed Buchwald-Hartwig amination conditions, a compound of formula (IX) (wherein R ¹ and X are as defined in formula (I), and R ¹² is a halogen, preferably bromine Or iodine) with a compound of formula (XI) (wherein R ² , R ³ , R ⁴ and R ⁵ are as defined in formula (I)). This is shown in Scheme 8 below.

Surprisingly, for practical use, it has been discovered that novel compounds of formula (I) have very favorable levels of biological activity and can be used to protect plants from diseases caused by fungi.

Compounds of formula (I) can be used in the agricultural sector and related fields as, for example, active ingredients for controlling plant pests, or on non-living materials for controlling spoilage microorganisms or organisms that are potentially harmful to humans. The novel compound has the characteristics of low use ratio but high activity, good plant tolerance and no harm to the environment. They have very useful therapeutic, preventive and systemic qualities and can be used to protect countless cultivated plants. Compounds of formula (I) can be used to inhibit or destroy pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of many different useful plant crops, while also protecting, for example, slightly Those plant parts that grow later are protected from phytopathogenic microorganisms.

The invention also relates to controlling or preventing plants or plant reproduction by treating plants or plant propagation material and / or harvested food crops in which an effective amount of a compound of formula (I) is applied to a plant, part thereof or its place Materials and / or methods for protecting harvested food crops that are susceptible to microbes.

It is also possible to use compounds of formula (I) as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount" means an amount of such a compound or a combination of such compounds capable of having an effect on fungal growth. The effects of control or modification include all deviations from natural development, such as killing, retarding, etc., and preventing barriers or other defensive structures from being included in or on plants that prevent fungal infections.

Compounds of formula (I) can also be used as seed dressings for treating plant propagation materials (such as seeds, such as fruits, tubers, or grains), or plant cuttings (such as rice) for protection against fungal infections or soil Plant disease-causing fungi. The propagation material can be treated with a composition comprising a compound of formula (I) before planting, for example the seeds can be applied before sowing.

It is also possible to apply the active ingredients according to the invention to cereals (coating) by soaking the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is planted, for example to the furrows of the seed during sowing. The invention also relates to such a method of treating plant propagation material, and to the plant propagation material so treated.

In addition, the compounds according to the present invention can be used to control fungi in related fields, such as in the protection of industrial materials (including wood and wood-related industrial products), in food storage, in hygiene Under management.

In addition, the present invention can also be used to protect non-living materials such as wood, wallboard and paint from fungal attack.

Compounds of formula (I), such as fungi and fungal vectors against diseases, and bacteria and viruses that cause plant diseases may be effective. Fungi and fungal vectors for these diseases, as well as bacterial and viral strains that cause plant diseases, such as: A. aureus, Alternaria spp, Aphanomyces spp, Ascochyta spp ), Aspergillus spp. (Including A. flavus, A. fumigatus, A. nidulans, A. niger, soil A. terrus), Aureobasidium spp. (Including A. pullulans), Blastomyces dermatitidis, Blumeria graminis, lettuce dish Bremia lactucae, Botryosphaeria spp. (Including B. dothidea, B. obtusa), Botrytis spp. (Including B. cinerea), Candida (including C. albicans, C. glabrata, C. krusei), grape teeth C. lusitaniae, C. parapsilosis, C. tropicalalis, Cephaloascus fragrans, Ceratocystis spp, tail (Cercospora spp.) (Including C.arachidicola), Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis), Cochliobolus spp, Colletotrichum spp. (including C. musae), Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Powdery mildew Erysiphe spp. (Including E. cichoracearum), Eutypa lata, Fusarium spp. (Including culmorum, Fusarium graminearum ( F.graminearum), F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. oxysporum .subglutinans), F.solani), Gaeumannomyces graminis, vines Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, plant rust Gymnosporangium juniperi-virginianae), Helminthosporium spp, Hemileia spp, Histoplasma spp. (Including H. capsulatum), Red line bacteria, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor (Mucor spp), Mycosphaerella spp. (Including M.graminicola, M. Pomi), Oncobasidium theobromaeon, Spruce (Ophiostoma piceae), Paracoccidioides spp, Penicillium spp. (Including P. digitatum, P. italicum), Mycobacterium Petrielli dium spp), Peronosclerospora spp. (including P. maydis, P. philippines and S. sorghum), Peronospora spp. (Phaeosphaeria nodorum), Phakopsora pachyrhizi, Phellinu igniarus, Phialophora spp, Phoma spp, Phoma spp. (Phomopsis viticola), Phytophthora spp. (Including P. infestans), Plasmopara spp. (Including P. halstedii), Grape P. viticola), Pleospora spp., Podosphaera spp. (Including P. leucotricha), Heguduo Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. (Including cucumber downy mildew) (P.cubensis), P.humuli), Pseudopeziza tracheiphila, Downy mildew (including barley P. hordei, P. recondita, P. striiformis, P. triticina), Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. (Including P. oryzae), Pythium spp. (Including P.ultimum), column Ramularia spp, Rhizoctonia spp, Rhizomocor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. ) (Including S. apiospermum and S. prolificans), Schizothyrium pomi, Sclerotinia spp, Sclerotium spp), Septoria spp (including S.nodorum, S. tritici), Sphaerotheca macularis, Sphaerotheca fusca) (Sphaerotheca fuliginea), Sporothorix, Stagonospora nodorum, Stemphyli um), Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. T. harzianum), T. pseudokoningii, T. viride), Trichophyton spp, Typhula spp, grape Uncinula necator, Urocystis, Ustilago, Ustilago (including V. inaequalis), Verticillium spp , And Xanthomonas spp.

Within the scope of the present invention, the target crops and / or useful plants to be protected generally include perennial and annual crops, such as berry plants such as blackberries, blueberries, cranberries, raspberries, and strawberries; cereals such as barley, maize (corn ), Millet, oats, rice, rye, sorghum triticale and wheat; fiber plants such as cotton, flax, hemp, jute and sisal; crops such as sugar and fodder beets, coffee, hops, mustard, canola (cards Nora), poppy, sugar cane, sunflower, tea and tobacco; fruit trees such as apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears and plums; grasses such as Bermuda grass, bluegrass, Bentgrass, yarrow, fescue, ryegrass, st. Augustine and flora and fauna; herbs such as basil, borage, chives, parsley, lavender, lovage, mint, oregano, parsley, rosemary, Sage and thyme; legumes such as soybeans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palm plants such as oil palm; Ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olives and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, okra, onion, pepper , Potatoes, pumpkin, rhubarb, spinach and tomato; and vines, such as grapes.

The term "useful plant" should be understood to include herbicides (such as bromoxynil) or herbicides (e.g., like HPPD inhibitors, ALS inhibitors, such as flusulfuron) due to conventional breeding methods or genetic engineering. (primisulfuron), prosulfuron and trifloxysulfuron, EPSPS (5-enol-acetone-shikimate-3-phosphate-synthase) inhibitor, GS (glutamine synthetase) ) Inhibitor or PPO (protoporphyrinogen oxidase) inhibitor) useful plant tolerant. One example of a crop that has become tolerant to imidazolinones such as azamethacin by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (Canola). Examples of crops that have been conferred resistance to multiple herbicides or multiple herbicide classes by genetic engineering methods include glyphosate and glufosinate-resistant corn varieties, which are available in RoundupReady®, Herculex I®, and LibertyLink® Commercially available under the brand name.

The term "useful plant" should be understood to also include useful plants that have been so transformed by use of recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as known from, for example, toxin-producing bacteria, in particular These are the bacteria of the genus Bacillus.

Examples of such plants are: YieldGard® (corn variety, showing CryIA (b) toxin); YieldGard Rootworm® (corn variety, showing CryIIIB (b1) toxin); YieldGard Plus® (corn variety, showing CryIA (b) and CryIIIB) (b1) toxin); Starlink® (corn variety, expressing Cry9 (c) toxin); Herculex I® (corn variety, expressing CryIF (a2) toxin and enzyme phosphin filaments that achieve tolerance to the herbicide glufosinate) N-acetyltransferase (PAT)); NuCOTN 33B® (cotton variety, showing CryIA (c) toxin); Bollgard I® (cotton variety, showing CryIA (c) toxin); Bollgard II® (cotton variety, Expresses CryIA (c) and CryIIA (b) toxins); VIPPCOT® (cotton varieties, expresses VIP toxins); NewLeaf® (potato varieties, expresses CryIIIA toxins); NatureGard® Agrisure® GT Advantage (GA21 glyphosate resistance), Agrisure® CB Advantage (Bt11 corn borer (CB) traits), Agrisure® Rw (corn rootworm characteristics), and Protecta®.

The term "crop" is understood to also include crop plants transformed by the use of recombinant DNA techniques capable of synthesizing one or more selectively acting toxins, such as known, for example, from toxin-producing bacteria, especially Bacillus Those of the genus.

Toxins that can be expressed by the transgenic plants include, for example, insecticidal proteins, such as insecticidal proteins from Bacillus subtilis or Bacillus Japanese beetle; or insecticidal proteins, such as delta-endotoxin, from Bacillus thuringiensis, For example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or plant insecticidal protein (Vip), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of nematode parasitic bacteria, such as Bacillus Genus or pathogenic bacteria, such as Corynebacterium radiata, Nematode pathogenic bacteria; toxins produced by animals, such as scorpion toxin, spider toxin, wasp toxin and other insect-specific neurotoxins; toxins produced by fungi, such as chain Mycotoxins; plant lectins, such as pea lectins, barley lectins, or snowdrop lectins; lectins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato patatin, hemiproteins Cysteine inhibitors, papain inhibitors; ribosomal inactivating protein (RIP), such as Hemp protein, corn-RIP, acacia toxin, loofah seed toxin, saponin toxin or xenorrhagic toxin, steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycoside-transferase , Cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers, such as sodium or calcium channel blockers, juvenile hormone esterases, diuretic receptors, hydrazone synthase, bibenzyl Synthetase, chitinase and glucanase.

In the context of the present invention, delta-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A should be understood as clearly also apparent Includes mixed toxins, truncated toxins, and modified toxins. Mixed toxins are produced recombinantly by new combinations of different regions of those proteins (see, for example, WO 02/15701). Truncated toxins such as truncated Cry1Ab are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In this amino acid substitution, it is preferred to insert a non-naturally occurring protease recognition sequence into the toxin, such as in the case of Cry3A055, the cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878, and WO 03/052073.

Methods for making such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI DNA and its preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxins included in the transgenic plants make the plants resistant to harmful insects. Such insects can exist in any taxonomic group of insects, but are especially commonly found in beetles (coleoptera), dipterous insects (diptera), and butterflies (lepidoptera).

Transgenic plant lines comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (corn variety, showing Cry1Ab toxin); YieldGard Rootworm® (corn variety, showing Cry3Bb1 toxin); YieldGard Plus® (corn variety, showing Cry1Ab and Cry3Bb1 toxin); Starlink® (corn variety, Expressing Cry9C toxin); Herculex I® (maize variety, expressing Cry1Fa2 toxin and the enzyme phosphinothricin N-acetamyltransferase (PAT) that achieves tolerance to the herbicide glufosinate); NuCOTN 33B® (cotton Variety, showing Cry1Ac toxin); Bollgard I® (cotton variety, showing Cry1Ac toxin); Bollgard II® (cotton variety, showing Cry1Ac and Cry2Ab toxin); VipCot® (cotton variety, showing Vip3A and Cry1Ab toxin); NewLeaf® (potato Variety, showing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate resistance), Agrisure® CB Advantage (Bt11 corn borer (CB)) and Protecta®.

Other examples of such GM crops are:

1. Bt11 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Genetically modified maize has been genetically modified to express truncated Cry1Ab toxins, making it resistant to attack by European corn borer (corn borer and pink stem borer). Bt11 corn also genetically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate.

2. Bt176 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Genetically modified maize, by transgenic expression of Cry1Ab toxin, makes it resistant to attack by European corn borer (corn borer and pink stem borer). Bt176 corn also genetically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate.

3. MIR604 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Insect-resistant corn by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic corn plants is described in WO 03/018810.

4. MON 863 corn from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02/9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

5. IPC 531 cotton from Monsanto Europe, 270-272 Teflon Avenue, B-1150 Brussels, Belgium, registration number C / ES / 96/02.

6. 1507 corn from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00/10. Genetically modified corn expresses the protein Cry1F to obtain resistance to certain Lepidoptera insects, and expresses the PAT protein to obtain tolerance to the herbicide glufosinate.

7. NK603 × MON 810 corn from Monsanto Europe, 270-272 Teflon Avenue, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. By crossing genetically modified varieties NK603 and MON 810, a hybrid corn variety of conventional breeding is constituted. NK603 × MON 810 corn transgene expresses CP4 EPSPS protein obtained from Agrobacterium strain CP4, makes it tolerant to herbicide Roundup® (containing glyphosate), and Cry1Ab toxin obtained from Bacillus thuringiensis Kurstak subsp. It is resistant to certain Lepidoptera insects, including the European corn borer.

The term "locus" as used herein refers to the place in or on which the plant is grown, or where the seeds of the cultivated plant are sown, or where the seeds are to be placed in the soil. It includes soil, seeds, and seedlings, along with established plants.

The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves and fruits.

The term "plant propagation material" should be understood to mean the reproductive parts of the plant, such as seeds, which can be used for the reproduction of the plant, as well as nutritional materials, such as cuttings or tubers (such as potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Mention may also be made of germinated plants and young plants that will be transplanted after germination or after soil breaking. The young plants can be protected before transplantation by full or partial treatment by dipping. Preferably, "plant propagation material" should be understood as meaning seeds.

Pesticides using their common names mentioned herein are known, for example, from the "Pesticide Manual", 15th edition, British Crop Protection Councii 2009.

The compound of formula (I) can be used in unmodified form or, preferably, with adjuvants conventionally used in the field of formulation. To this end, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, Dust, particles, and also encapsulations, for example, in polymeric substances. For the type of such composition, the application method is selected according to the intended purpose and prevailing environment, such as spraying, atomizing, dusting, spreading, coating or pouring. These compositions may also contain additional adjuvants, such as stabilizers, defoamers, viscosity modifiers, adhesives or tackifiers, as well as fertilizers, micronutrient donors, or other formulations for obtaining special effects.

Suitable carriers and adjuvants, for example for agricultural use, can be solid or liquid and are useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersions, wetting agents, tackifiers, Thickeners, binders or fertilizers. Such vectors are described, for example, in WO 97/33890.

The compound of formula (I) is generally used in the form of a composition and can be applied to the crop area or the crop to be treated simultaneously or sequentially with another compound. For example, such additional compounds may be fertilizers or micronutrient donors or other agents that affect plant growth. They can also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these formulations, if desired with the formulation Together with additional carriers, surfactants or adjuvants that facilitate administration.

The compounds of formula (I) can be used in the form of a composition that controls or protects against phytopathogenic microorganisms (fungicidal), which compositions comprise at least one compound of formula (I) or at least one preferred The individual compounds as defined above are used as active ingredients (in free form or in the form of agriculturally useful salts) and include at least one of the above-mentioned adjuvants.

The present invention provides the following composition, preferably a fungicidal composition, comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Such agricultural carriers are well known in the art. Preferably, in addition to including a compound of formula (I), the composition may include at least one or more pesticidally active compounds, such as additional fungicidal active ingredients.

The compound of formula (I) may be the sole active ingredient of the composition, or it may be combined with one or more additional active ingredients (e.g., a pesticidal, fungicide, synergist, herbicide, or plant growth regulator, as appropriate) Agent) mixed. In some cases, additional active ingredients can lead to unexpected synergistic activity.

Examples of suitable additional active ingredients include the following acycloamino acid fungicides, aliphatic nitrogen fungicides, amidine fungicides, aniline fungicides, antibiotic fungicides, aromatic fungicides Agents, arsenic-containing fungicides, aryl phenone fungicides, benzamidine fungicides, benzamidine aniline fungicides, benzimidazole fungicides, benzothiazole fungicides, plant fungicides Agent, bridging biphenyl fungicide, carbamate fungicide, aniline fungicide, conazole fungicide, copper fungicide, dimethylformimide fungicide, dinitrate Phenol fungicide, dithiocarbamate fungicide, dithiopentan fungicide, furfuran fungicide, furfuran fungicide, hydrazine fungicide, imidazole fungicide, mercury Fungicides, Porphyrin fungicides, organophosphate fungicides, organotin fungicides, oxathiin fungicides, Azole fungicides, thiothiazide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungi Agents, quinone fungicides, quinoxaline fungicides, oleophyllin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, tetrahydrothiazole fungicides Agents, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide Fungicides, and zinc fungicides.

Examples of suitable additional active ingredients also include the following: 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4- Tetrahydro-1,4-methylidene-naphthalene-5-yl) -amidamine, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy- [1-methyl- 2- (2,4,6-trichlorophenyl) -ethyl] -amidamine, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (2-dichloromethylene 3-Ethyl-1-methyl-dihydroinden-4-yl) -amidamine (1072957-71-1), 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (4'-methylsulfonyl-biphenyl-2-yl) -amidamine, 1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid [2- (2,4- Dichloro-phenyl) -2-methoxy-1-methyl-ethyl] -amidamine, (5-chloro-2,4-dimethyl-pyridin-3-yl)-(2,3, 4-trimethoxy-6-methyl-phenyl) -methanone, (5-bromo-4-chloro-2-methoxy-pyridin-3-yl)-(2,3,4-trimethoxy -6-methyl-phenyl) -methanone, 2- {2-[(E) -3- (2,6-dichloro-phenyl) -1-methyl-prop-2-ene- (E ) -Iminoaminooxymethyl] -phenyl} -2-[(Z) -methoxyimino] -N-methyl-acetamide, 3- [5- (4-chloro- (Phenyl) -2,3-dimethyl-iso Azolidine-3-yl] -pyridine, (E) -N-methyl-2- [2- (2,5-dimethylphenoxymethyl) phenyl] -2-methoxy-imine Ethylacetamide, 4-bromo-2-cyano-N, N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide, a- [N- (3-chloro-2,6- Xylyl) -2-methoxyacetamido] -y-butyrolactone, 4-chloro-2-cyano-N, -dimethyl-5-p-tolylimidazole-1-sulfonamide, N -Allyl-4,5, -dimethyl-2-trimethylsilylthiophene-3-carboxamide, N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propanamide, N- (2-methoxy-5-pyridyl) -cyclopropaneformamide, (. +-.)-Cis-1- (4- (Chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -cycloheptanol, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3 -(1,2,4-triazol-1-yl) -propan-2-ol, 2 ', 6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl -1,3-thiazole-5-carboxanilide, 1-imidazolyl-1- (4'-chlorophenoxy) -3,3-dimethylbut-2-one, methyl (E)- 2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylate, methyl (E) -2- [2- [6- (2-thioaminophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-fluorobenzene (Oxy) pyrimidin-4-yloxy Phenyl] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) -phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (phenyl-sulfonyloxy) phenoxy] phenyl-3-methoxyacrylate, methyl (E) -2- [2- [3- (4-nitro Phenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E ) -2- [2- (3,5-dimethyl-benzylidene) pyrrole-1-yl] -3-methoxyacrylate, methyl (E) -2- [2- (3- Methoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2 [2- (2-phenylethen-1-yl) -phenyl] -3-methoxy Acrylate, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2 -(3- (1,1,2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl (E) -2- (2- [3- ( α-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl (E) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n Propyloxy-phenoxy) phenyl] 3-methoxyacrylate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methyl Methacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2 -[2- (3-ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butyl-pyridin-2-yl (Oxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxy Acrylate, methyl (E) -2- [2-[(3-methyl-pyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E)- 2- [2- [6- (2-methyl-phenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- ( 5-bromo-pyridine-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) (Phenyl) phenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy Phenyl] phenyl] -3-methoxyacrylate, methyl (E), (E) -2- [2 -(5,6-dimethylpyridine 2-ylmethyloximemethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- {2- [6- (6-methylpyridin-2-yloxy) Pyrimidin-4-yloxy] phenyl} -3-methoxy-acrylate, methyl (E), (E) -2- {2- (3-methoxyphenyl) methyloximemethyl Group] -phenyl} -3-methoxyacrylate, methyl (E) -2- {2- (6- (2-azidophenoxy) -pyrimidin-4-yloxy] phenyl } -3-methoxyacrylate, methyl (E), (E) -2- {2- [6-phenylpyrimidin-4-yl) -methyloximemethyl] phenyl} -3- Methoxyacrylate, methyl (E), (E) -2- {2-[(4-chlorophenyl) -methyloximemethyl] -phenyl} -3-methoxyacrylate, Methyl (E) -2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylic acid Lipid, methyl (E), (E) -2- {2-[(3-nitrophenyl) methyloximemethyl] phenyl} -3-methoxyacrylate, 3-chloro-7 -(2-aza-2,7,7-trimethyl-oct-3-ene-5-base), 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzyl Amidine, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropynyl formal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate , 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propanol, 3-iodo-2-propyne N-butylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo-2-propynylcyclohexyl-carbamate, 3-iodo-2 -Propynylphenylcarbamates; phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxy Ethanol, dichlorophenol, o-phenylphenol, m-phenyl-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol, 5-hydroxy-2 (5H) -furanone; 4,5 -Dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro- (3H) -1,2-dithio 1 -3-one, 3,5-dimethyl-tetrahydro-1,3,5-thiadi 2-thione, N- (2-p-chlorobenzylethyl) -hexamethylenetetramine chloride, acibenzolar, acypetacs, alanycarb, albenta Albendazole, aldimorph, allicin, allyl alcohol, ametoctradin, amisulbrom, amobam, amphetamine Acid (ampropylfos), anilazine, asomate, aureofungin, azaconazole, azafendin, azithiram , Azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, enemy Benquinox, Bentaluron, Benthiavalicarb, Benthiazole, Benzalconium Chloride, Benzamacril, Benzox (benzamorf), benzohydroxamic acid, benzovindiflupyr, berberine, bethoxazin, biphenyltriazol (bi loxazol), binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin- S (blasticidin-S), boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine polysulfide Butylamine calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim chlorhydrate, carbendazim carboxin, carpropamid, carvone, CGA41396 (CGA41396), CGA41397 (CGA41397), chinomethionate, chitosan, chlobenthiazone (chlobenthiazone) , Chloraniformethan, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, ethyl Chlozolinate, climazole, clotrimazole, clozylacon, Copper compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, oxygen Copper oxyquinolate, copper silicate, copper sulfate, copper tallate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, copper Cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil , Cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid , Di-2-pyridyl disulfide 1,1'-dioxide, dichlofluanid, diclomezine, dichlohe, dichlorolan, dichloro Dichlorophen, dichlozoline, diclobutrazol, dichlorobutrazol Diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-diiso-propyl-S-benzyl Dithiophosphate, Dimefluazole, Dimetachlone, Dimetconazole, Dimethonazole Dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos , Dithianon, dithioether, dodecyl dimethyl ammonium chloride, dodecyl ring Dodemorph, dodicin, dodine, doguadine, drazoxolon, edifenphos, enestroburin ), Epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin Ethyl (Z) -N-benzyl-N ([methyl (methyl-thioethyleneamino-oxycarbonyl) amino] thio) -ß-aminopropionic acid ethyl ester, earth Etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, Fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin (fenpicamid) fenpropidin), styrene butadiene Fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluridine Fluazinam, fludioxonil, flumetover, fluorine Flumorph, flupioolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole ), Flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluapyroxad, folpet ), Formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole ), Furfural, furmecyclox, furophanate, glyodin, greoeofulvin, guazatine, quinacrylic acid (halacrinate), Hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaeonazole, hexylthiofos, hydrargaphen, hydroxyiso Hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine, triacetin (iminoctadine triacetate), inezin, iodocarb, ipconazole, ipfentritluconazole, iprofenfos, isoprofen Iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isopyrazam (isopyrazam) isotianil), isovaledione, izopamfos, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb , Mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam, mefentrifluconazole, Mepanipyrim, mepronil, mercuric chloride, chlorine Mercurous chloride, meptyldinocap, metalaxyl, metalaxyl-M, metam, hydrazine Metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate ( methyl isothiocyanate, metiram, metiram-zinc, metominostrobin, metrafenone, metsulfovax, milenb , Moroxydine, myclobutanil, myclozolin, nabam, natamycin, neoasozin, nickel dimethyldithiocarbamate, nitrobenzene Ethylene (nitrostyrene), nitrothal-iso-propyl, nuarimol, octhilinone, ofurace, organic mercury compounds, orysastrobin ), Osthol, Oxadixyl, oxasulfuron, oxathiapiprolin, oxine-copper, Oxolinic acid, oxpoconazole, oxycarboxin, parinol, pefurazoate, penconazole, pencycuron , Penflufen, pentachlorophenol, penthiopyrad, phenamacril, phenazin oxide, phosdiphen, Phytophthora Phosetyl-Al, phosphoric acids, phthalide, picoxystrobin, piperalin, polycarbamate, polyox Polyoxin D, polyoxrim, polyram, probenazole, prochloraz, promidmidone, propamidine , Propamocarb, propiconazoie, propineb, propionic acid, proquinazid, prothiocarb, prothioconazole ), Pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametrost robin), pyraoxystrobin, pyrazophis, pyribencarb, pyridinitril, pyrifenox, pyrimimethanil, piofenone (pyriofenone), pyroquilon, pyroxychlor, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinacetol ), Quinazamid, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenzazole, artemisinin ( santonin, sedaxane, silthiofam, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine Streptomycin, sulphur, sultropen, tebuconazole, tebfloquin, tecloftalam, tetrachloronitrobenzene ( tecnazene), tecoram, tetraconazole, thiabendaz ole), thiadifluor, thicyofen, thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiocarbam -Thiophanate-methyl, thioquinox, thiram, tiadinil, timibenconazole, tioxymid, ritaphon -Methyl (tolclofos-methyl), tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, butadiazole triazbutil), triazoxide, tricyclazole, thirteen Trinemorph, trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole, uniconazole, formamidine urbacide, validamycin, valifenalate, vapam, vinclozolin, zarilamid, zineb, ziram ) And zoxamide.

The compounds of the present invention can also be used in combination with a worm repellent. Such helminthicides include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamitin, emamectin, edamectin Eprinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as in EP -357460, EP-444964 and EP-594291. Other worm-repelling agents include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US-5015630, WO-9415944, and WO-9522552. Other helminthicides include benzimidazoles, such as albendazole, cambendazole, febendazole, flubendazole, and mebendazole , Oxfendazole, oxibendazole, parbendazole, and other members of this category. Other helminthicides include imidazothiazolyls and tetrahydropyrimidines, such as tetraimidazole, levamisole, thianehydropyrimidine, oxantel or morantel. Other helminthicides include insecticides, such as trichlorobendazole and losulone, as well as insecticides, such as praziquantel and exemestil.

The compound of the present invention can be used with derivatives and analogues of parabenamine para-penicillium penicillamine / marcfortine worm repellent agents and antiparasites An oxazoline (such as disclosed in US-5478855, US-4639771, and DE-19520936) is used in combination.

The compounds of the invention can be combined with the general kind of dioxygen as described in WO-9615121 Derivatives and analogs of morpholine antiparasitic agents and cyclic acetal peptides that are also active against worms EP-382173, and those described in EP-503538) are used in combination.

The compounds of the present invention can be used in combination with other ectoparasite killers; for example, fipronil; pyrethroids; organic phosphates; insect growth regulators (e.g., lufenuron); ecdysone agonists (e.g., insecticides Hydrazine and its analogs); neonicotinoids (such as imidacloprid and its analogs).

The compounds of the invention can be used in combination with terpene alkaloids, such as those described in WO 95/19363 or WO 04/72086, especially the compounds disclosed therein.

Other examples of such biologically active compounds that can be used in combination with the compounds of the invention include, but are not limited to, the following: organic phosphates: acephate, methylpyridine Azamethiphos, azonphos-ethyl, azonphos-methyl, bromophos, bromophos-ethyl, cadusafos ), Chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl ), Demeton-S-methyl sulphone, dilifos, diazinon, dichlorvos, dicrotophos, dimethoate (dimethoate), disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion (fenitrothion), fensulfothion, fenthion, flupyrazofos, fonofos, forthion, fosthiazate, heptenophos ), Isazophos, isothioate, isopropyl Isoxathion, malathion, methacriphos, metamidophos, methathion, methyl-parathion, and quick-release phosphorous mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion , Methyl parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamine (phosphamidon), phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propaphos , Proetamphos, prothiofos, pyraclofos, Pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos , Thimeton, triazophos, trichlorfon, vamidothion.

Carbamates: alanycarb, aldicarb, 2-secondary butylphenylmethylcarbamate, benfuracarb, carbaryl, Carbofuran, carbosulfan, clothothocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb ), HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-isopropylphenylbutynyl (methyl ) Carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC- 51717.

Pyrethroids: acrithrin, allethrin, alpha-metrin, 5-benzyl-3-furylmethyl (E)-(1R) -cis -2,2-Dimethyl-3- (2-oxetane-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin , Cyfluthrin, α-cypermethrin, β-cypermethrin, bioallethrin, bioallethrin ((S) -cyclopentyl isomer ), Bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin ), Deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin , Fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, chlorine Cyhalothrin, λ-chlorofluoro Lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural product), resmethrin , Tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, t-fluvalinate, Tefluthrin, tralomethrin, Zeta-cypermethrin.

Arthropod growth regulators: a) Chitin synthesis inhibitor: Benzamuron: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufluxuron (flufenoxuron), hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, fenprofen (diofenolan), hexythiazox, etoxazole, clofentazin; b) ecdysone antagonists: chlorantrazine, methamphetamine, carbazid; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), phenoxycarb; d) lipid biosynthesis inhibitor: spirotetramat.

Other antiparasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, and Bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlorbenzilate Chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI -3204, dinactin, dihydroxymethyl dihydroxy pyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethiprole (ethofenprox), fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate , Flufenzine, flufenprox, fluproxyfen, halofenprox, fluoroants Hydramethylnon, IKI-220, sodalite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477 , Acetamiprid, clotrim, protrifenbute, pyrmethrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345 , RH-2485, RRI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, tebufenpyrad, three Tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, Triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301.

Biological agents: Bacillus thuringiensis ssp aizawai, Bacillus thuringiensis ssp aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, viruses, and fungi.

Bactericides: chlortetracycline, oxytetracycline, streptomycin.

Enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, piriprole, cefquinome, fluorine Florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone , Praziquarantel, trilabendazole.

Another aspect of the present invention relates to a compound of formula (I), or preferably a separate compound as defined above, including at least one compound of formula (I) or at least one preferred individual as defined above Fungicidal or bactericidal as defined above in combination with other fungicides or insecticides, comprising at least one compound of formula (I) or at least one preferred individual compound as defined above Use of insect mixtures to control or prevent plants (e.g. useful plants (e.g. crops)), their propagation materials (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living materials from insects or Infection by phytopathogenic microorganisms, preferably fungal organisms.

Another aspect of the invention relates to controlling or preventing plants (e.g. useful plants (e.g. crops)), their propagating material (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living materials from insects or Method for infecting plant disease-causing or spoilage microorganisms or potentially harmful organisms (especially fungal organisms), which method comprises using a compound of formula (I) or preferably a separate compound as defined above as an active ingredient Applied to such plants, parts of plants or to their bottoms, their propagation material, or any part of non-living material.

Controlling or preventing means reducing the infestation by insects or phytopathogenic or spoilage microorganisms or organisms that are potentially harmful to humans, especially fungal organisms, to such a proven level.

A preferred method for controlling or preventing crops from being infected by phytopathogenic microorganisms (especially fungi) or insects is foliar application, which comprises applying a compound of formula (I), or an agrochemical containing at least one of said compounds组合 物。 Composition. The frequency and rate of application will depend on the risk of infection by the corresponding pathogen or insect. However, the compound of formula (I) can also be passed through the soil via the roots by soaking the bottom of the plant with a liquid formulation or by applying the compound in solid form, for example in the form of granules (soil application) to the soil. Systemic action) penetrates the plant. In rice crops, such particles can be applied to irrigated rice fields. The compound of formula (I) can also be applied to seeds (coatings) by impregnating seeds or tubers with a liquid formulation of a fungicide or coating it with a solid formulation.

Formulations, such as those comprising a compound of formula (I), and (if desired) a solid or liquid adjuvant or a monomer for encapsulating the compound of formula (I), can be in a known manner, typically It is prepared by intimately mixing and / or grinding the compound with extenders such as solvents, solid carriers, and optionally surface-active compounds (surfactants).

Advantageous application rates are usually from 5 g to 2 kg of active ingredient (a.i.) / Ha (ha), preferably from 10 g to 1 kg a.i./ha, and most preferably from 20 g to 600 g a.i./ha. When used as a seed soaking agent, a suitable dosage is from 10 mg to 1 g of active substance / kg of seed.

When the combination according to the invention is used to treat seeds, a ratio of 0.001 g to 50 g of the compound of formula (I) per kg of seed, preferably from 0.01 g to 10 g / kg of seed, is generally sufficient.

The composition of the present invention can be used in any conventional form, for example, having double packaging, powder for dry seed treatment (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), Seed treatment solution (LS), seed treatment water dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension Concentrate (SC), suspension emulsion (SE), capsule suspension (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsion (EO), oil-in-water type Emulsion (EW), microemulsion (ME), dispersing oil suspension (OD), oil suspension (OF), oil-soluble liquid agent (OL), soluble concentrate (SL), ultra-low-volume suspension agent (SU) , Ultra-low-volume liquid (UL), parent drug (TK), dispersible concentrate (DC), wettable powder (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants form.

Such compositions can be produced in a conventional manner, for example, by mixing the active ingredients with appropriate formulated inerts (diluents, solvents, fillers and optionally other formulated ingredients, such as surfactants, biocides, antifreeze, adhesion Agents, thickeners and compounds that provide adjuvant effects). It is also possible to use conventional sustained-release formulations, which are intended to last a long time. In particular, formulations to be applied in the form of sprays, such as water-dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as Wetting and dispersing agents and other compounds that provide adjuvant effects, such as formaldehyde and naphthalenesulfonates, alkarylsulfonates, ligninsulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylates Condensation product of a fatty alcohol.

Using the combination and diluent of the present invention, the seed dressing formulation is applied to the seed in a suitable seed dressing formulation form, such as an aqueous suspension or dry powder having good adhesion to the seed, in a manner known per se . Such seed dressing formulations are known in the art. Such seed dressing formulations may contain a single active ingredient or a combination of active ingredients in the form of a sealant, such as a sustained release capsule or microcapsule.

Generally, formulations include from 0.01% to 90% by weight of active ingredients, from 0 to 20% of agriculturally acceptable surfactants, and from 10 to 99.99% of solid or liquid formulation inerts and one or more adjuvants. The active agent is composed of a compound of at least formula (I) together with components (B) and (C), and optionally other active agents (especially microbicides or preservatives or the like). The concentrated form of the composition typically comprises between about 2% and 80% by weight, preferably between about 5% and 70% of the active agent. The formulation may be applied by weight, for example, from 0.01% to 20%, preferably from 0.01% to 5% of the active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will typically use diluted formulations.

[Example]

The following examples serve to illustrate the invention: The compounds of the invention may be distinguished from known compounds by greater efficacy at low application rates, which can be used by those skilled in the art to use the experiments outlined in the examples Procedure, using lower application rates (if necessary), for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm, or 0.2 ppm to confirm.

Compounds of formula (I) can have any number of benefits, including in particular a favorable level of biological activity directed at protecting plants against diseases caused by fungi or superior properties for use as active ingredients in agricultural chemicals (e.g., higher biological Activity, favorable range of activity, increased safety (including improved crop tolerance), improved physical-chemical properties, or increased biodegradability).

Example 1: This example illustrates N- (1-cyano-1,2-dimethyl-propyl) -2- (3,5-difluoroaniline) -5-methyl-thiazole-4- Preparation of formamidine (compound 1.n.3)

a) Preparation of methyl 2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxylate

A mixture of methyl 2-bromo-5-methyl-thiazole-4-formate (5.0 g, 20 mmol) and 3,5-difluoroaniline (13.3 g, 101 mmol) was heated to 130 ° C. with stirring for 1 h . The reaction mixture was cooled to room temperature and diluted with ethyl acetate and water. The phases were separated, the aqueous phase was extracted with ethyl acetate, the combined organic layers were washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and heptane as eluents to give methyl 2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxylate (4.9 g, 17 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 2.73 (s, 3H), 3.94 (s, 3H), 6.52 (t, 1H), 6.86 (d, 2H), 7.43 (bs, 1H).

b) Preparation of 2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxylic acid

Lithium hydroxide monohydrate (1.7 g, 69 mmol) was added to methyl 2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxylic acid in a mixture of 40 ml of tetrahydrofuran and 20 ml of water Ester (4.9 g, 17 mmol) in solution. The reaction mixture was stirred at room temperature for 16 h, and then the solvent was removed in vacuo. The residue was diluted with ethyl acetate and water, and then 2N hydrochloric acid was slowly added until the pH was 3-4. The insoluble solid was removed from the biphasic mixture by filtration and the first desired product was obtained. The different phases of the filtrate were separated, the aqueous phase was extracted with ethyl acetate, the combined organic layers were washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure to give the second portion of the desired product. The two solid batches were combined and dried under high vacuum to give 2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxylic acid (4.6 g, 16 mmol). ¹ H-NMR (400 MHz, MeOD): δ = 2.69 (s, 3H), 6.51 (t, 1H), 7.30 (d, 2H).

c) N- (1-cyano-1,2-dimethyl-propyl) -2- (3,5-difluoroaniline) -5-methyl-thiazole-4-carboxamide (Compound In 3) Preparation

Triethylamine (0.22 g, 2.22 mmol) and propanephosphonic anhydride (T3P, 0.94 g, 1.48 mmol) were continuously added to 2- (3,5-difluoroaniline) -5-methyl in 10 ml of acetonitrile -A solution of thiazole-4-carboxylic acid (0.2 g, 0.74 mmol). The reaction mixture was stirred at room temperature for 30 min, and then 2-amino-2,3-dimethylbutyronitrile (0.1 g, 0.89 mmol) was added. Stirring was continued for 16 h at room temperature, then the reaction mixture was diluted with ethyl acetate, washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and heptane as eluents to obtain N- (1-cyano-1,2-dimethyl-propyl) -2- (3,5- Difluoroaniline) -5-methyl-thiazole-4-carboxamide (Compound In3, 0.14 g, 0.36 mmol). ¹ H-NMR (400MHz, CDCl ₃ ): δ = 1.19 (d, 3H), 1.25 (d, 3H), 1.78 (s, 3H), 2.39 (hep., 1H), 2.78 (s, 3H), 6.54 (t, 1H), 6.96-7.02 (m, 2H), 7.40 (bs, 1H).

Example 2: This example illustrates 5-bromo-N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline) thiazole-4-carboxamide (compound 1.e.2) Preparation

a) Preparation of ethyl 2- (3,5-difluoroaniline) thiazole-4-carboxylate

Potassium phosphate (1.9 g, 8.7 mmol), tris (dibenzylideneacetone) dipalladium (0.27 g, 0.29 mmol), Xantphos (0.17 g, 0.29 mmol) and 3,5-difluoroiodobenzene (1.5 g, 6.4 mmol) were successively added to a mixture of ethyl 2-aminothiazole-4-formate (1.0 g, 5.8 mmol) in a mixture of 9 ml of toluene and 3 ml of water. The mixture was flushed with argon for 20 minutes and then heated in a microwave to 140 ° C for 1 hour. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and water, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and cyclohexane as eluents to give ethyl 2- (3,5-difluoroaniline) thiazole-4-carboxylic acid ester (0.16 g, 0.56 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.41 (t, 3H), 4.40 (q, 2H), 6.54 (t, 1H), 6.95 (d, 2H), 7.63 (s, 1H).

b) Preparation of 2- (3,5-difluoroaniline) thiazole-4-carboxylic acid

Lithium hydroxide monohydrate (54 mg, 2.2 mmol) was added to ethyl 2- (3,5-difluoroaniline) thiazole-4-carboxylate (0.16 g, 0.56) in a mixture of 2 ml of tetrahydrofuran and 1 ml of water. mmol) in solution. The reaction mixture was stirred at room temperature for 16 h, and then the solvent was removed in vacuo. The residue was diluted with water and then 2N hydrochloric acid was slowly added until the pH reached 3-4. The mixture was extracted with ethyl acetate, and the organic layer was washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure to give 2- (3,5-difluoroaniline) thiazole-4-carboxylic acid (98 mg, 0.38 mmol). ¹ H-NMR (400 MHz, MeOD): δ = 6.52 (t, 1H), 7.33 (d, 2H), 7.72 (s, 1H).

c) Preparation of N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline) thiazole-4-carboxamide

Triethylamine (49mg, 0.48mmol) and propanephosphonic anhydride (T3P, 0.2g, 0.32mmol) were continuously added to 5ml of acetonitrile 2- (3,5-difluoroaniline) thiazole-4-carboxylic acid (47mg , 0.16 mmol). The reaction mixture was stirred at room temperature for 30 minutes, and then 1-cyclohexylethylamine (24 mg, 0.19 mmol) was added. Stirring was continued for 16 h at room temperature, then the reaction mixture was diluted with ethyl acetate, washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and cyclohexane as eluents to obtain N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline) thiazole-4 -Formamidine (29 mg, 0.08 mmol). ¹ H-NMR (400MHz, CDCl ₃ ): δ = 1.02-1.13 (m, 4H), 1.20 (d, 3H), 1.48 (q, 1H), 1.65-1.82 (m, 6H), 4.03 (q, 1H ), 6.55 (t, 1H), 7.03 (d, 2H), 7.55 (s, 1H).

d) Preparation of 5-bromo-N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline) thiazole-4-carboxamide (compound 1.e.2)

N-bromosuccinimide (12 mg, 0.07 mmol) was added to N- (1-cyclohexylethyl) -2- (3,5- in 2 ml of N, N-dimethylformamide) Difluoroaniline) thiazole-4-carboxamide (23 mg, 0.06 mmol). The reaction mixture was stirred at room temperature for 1 hour, then diluted with ethyl acetate and washed with water. The organic layer was dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and cyclohexane as eluents to obtain 5-bromo-N- (1-cyclohexylethyl) -2- (3,5-difluoroaniline ) Thiazole-4-carboxamide (Compound Ie2, 18 mg, 0.04 mmol). ¹ H-NMR (400MHz, CDCl ₃ ): δ = 1.01-1.18 (m, 4H), 1.21 (d, 3H), 1.48 (q, 1H), 1.67-1.83 (m, 6H), 3.99 (q, 1H ), 6.54 (t, 1H), 7.06 (d, 2H).

Table 1 below shows examples of the individual compounds of formula (I) according to the invention.

among them

a) 80 compounds of formula (Ia):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

b) 80 compounds of formula (Ib):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

c) 80 compounds of formula (Ic):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

d) 80 compounds with chemical formula (Id):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

e) 80 compounds of formula (Ie):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

f) 80 compounds with chemical formula (If):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

g) 80 compounds of formula (Ig):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

h) 80 compounds of formula (Ih):

Wherein R ^1, R ^2, R ³ and X are as in Table 1 based defined.

i) 80 compounds of formula (Ii):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

j) 80 compounds of formula (Ij):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

k) 80 compounds of formula (Ik):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

m) 80 compounds having the chemical formula (Im):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

n) 80 compounds with chemical formula (In):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

o) 80 compounds of formula (Io):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

p) 80 compounds of formula (Ip):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

q) 80 compounds of formula (Iq):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

r) 80 compounds of formula (Ir):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

s) 80 compounds with chemical formula (Is):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

t) 80 compounds with chemical formula (It):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

u) 80 compounds of formula (Iu):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

v) 80 compounds of formula (Iv):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

w) 80 compounds of formula (Iw):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

x) 80 compounds of formula (Ix):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

y) 80 compounds of formula (Iy):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

z) 80 compounds of formula (Iz):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

aa) 80 compounds of formula (I.aa):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ab) 80 compounds having the chemical formula (I.ab):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ac) 80 compounds of formula (I.ac):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ad) 80 compounds of formula (I.ad):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ae) 80 compounds of formula (I.ae):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

af) 80 compounds of formula (I.af):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ag) 80 compounds of formula (I.ag):

Wherein R ^1, R ^2, R ³ and X are as in Table 1 based defined.

ah) 80 compounds of the formula (I.ah):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ai) 80 compounds having the chemical formula (I.ai):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

aj) 80 compounds of formula (I.aj):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ak) 80 compounds having the chemical formula (I.ak):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

am) 80 compounds of formula (I.am):

Wherein R ^1, R ^2, R ³ and X are as in Table 1 based defined.

an) 80 compounds having the chemical formula (I.an):

Wherein R ^1, R ^2, R ³ and X are as in Table 1 based defined.

ao) 80 compounds having the chemical formula (I.ao):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ap) 80 compounds having the chemical formula (I.ap):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

aq) 80 compounds of formula (I.aq):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ar) 80 compounds of formula (I.ar):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

as) 80 compounds having the chemical formula (I.as):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

at) 80 compounds having the chemical formula (I.at):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

au) 80 compounds of formula (I.au):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

av) 80 compounds of formula (I.av):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

aw) 80 compounds of formula (I.aw):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ax) 80 compounds of formula (I.ax):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ay) 80 compounds having the chemical formula (I.ay):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

az) 80 compounds having the chemical formula (I.az):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

ba) 80 compounds having the chemical formula (I.ba):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bb) 80 compounds of formula (I.bb):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bc) 80 compounds of formula (I.bc):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bd) 80 compounds of formula (I.bd):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

be) 80 compounds having the chemical formula (I.be):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bf) 80 compounds of formula (I.bf):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bg) 80 compounds of formula (I.bg):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bh) 80 compounds of formula (I.bh):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bi) 80 compounds of formula (I.bi):

Wherein R ^1, R ^2, R ³ and X are as in Table 1 based defined.

bj) 80 compounds of formula (I.bj):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

bk) 80 compounds of formula (I.bk):

Where R ¹ , R ² , R ³ and X are as defined in Table 1.

Throughout this specification, temperatures are given in degrees Celsius (° C) and "mp" refers to the melting point. LC / MS refers to liquid chromatography mass spectrometry, and the description and method of the device are: (ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 μm particle size, 110 Angström, 30 x 3 mm column, 1.7 mL / min, 60 ℃, H ₂ O + 0.05% HCOOH (95%) / CH ₃ CN / MeOH 4: 1 + 0.04% HCOOH (5%)-2min-CH ₃ CN / MeOH 4: 1 + 0.04% HCOOH (5%)-0.8min, ACQUITY SQD mass spectrometer from Waters, Ionization method: Electrospray (ESI), Polarity: Positive ion, Capillary voltage (kV) 3.00, Taper voltage (V) 20.00 , Extractor (V) 3.00, source temperature (° C) 150, desolvation temperature (° C) 400, tapered backflush gas flow (L / Hr) 60, desolvation gas flow (L / Hr) 700)).

Formulation examples

The active ingredient is thoroughly mixed with the adjuvant and the mixture is sufficiently ground in an appropriate mill, thereby obtaining a wettable powder which can be diluted with water to give a suspension of a desired concentration.

The active ingredient is thoroughly mixed with the adjuvants and the mixture is sufficiently ground in a suitable mill to provide a powder which can be directly used for seed treatment.

Emulsifiable concentrate

Active ingredient [Compound of formula (I)] 10%

Emulsions with any required dilution which can be used in plant protection can be obtained from this concentrate by dilution with water.

A ready-to-use powder is obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such powders can also be used in dry dressings of seeds.

Extruder granules

The active ingredient is mixed with these adjuvants and ground, and the mixture is moistened with water. The mixture was extruded and then dried in a stream of air.

Coated granules

This finely ground active ingredient is evenly applied in a mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

Suspension concentrate

The finely ground active ingredient is intimately mixed with the adjuvant to obtain a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. With such dilutions, live plants can be treated along with plant propagation material and protected from microbial infestation by spraying, pouring or dipping.

Flowable concentrate for seed treatment

The finely ground active ingredient is intimately mixed with the adjuvant to obtain a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. With such dilutions, live plants can be treated along with plant propagation material and protected from microbial infestation by spraying, pouring or dipping.

Sustained-release capsule suspension

A combination of 28 parts of the compound of formula (I) with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate-mixture (8: 1) were mixed. This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size was reached. To this emulsion was added 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water. The mixture was stirred until the polymerization reaction was completed.

The obtained capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation includes 28% of the active ingredient. The diameter of the media capsule is 8 micrometers to 15 micrometers.

The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

Biological Examples

Alternaria solani / tomato / leaf disc (premature blight)

Tomato leaf disc cultivar Betty (cv. Baby) was placed on agar in a multiwell plate (24 well format) and sprayed with a test compound formulated with DMSO and Tween20 and diluted in water. 2 days after application, the leaf discs were inoculated with a spore suspension of the fungus. Inoculated leaf discs were cultured in a climatic chamber at a light scheme of 12 / 12h (lighting / darkness) at 23 ° C / 21 ° C (day / night) and 80% relative humidity (rh), and untreated When appropriate levels of disease damage occurred in the control leaf discs (5-7 days after application), the activity of the compounds was evaluated as a percentage of disease control when compared to untreated.

Compounds Ia3, Ie3, Ir3, Is3, Iy1, Iy3, I at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions .ac.3, Is43, I.ao.3, I.au.3, I.at.3, I.bb.3 and I.bb.43 gave at least 80% of disease control in this trial.

Wheat powdery mildew (Blumeria graminis f.sp.tritici ) (Erysiphe graminis f.sp.Tritici ) / wheat / leaf disc prevention method (white powdery mildew on wheat)

The wheat leaf fragment cultivar Kansler (cv. Kanzler) was placed on agar in a multiwell plate (24 well format), sprayed with a test compound formulated with DMSO and Tween20, and diluted in water. One day after application, leaf discs were inoculated by shaking powdery mildew-infected plants above the test plates. In a climate chamber, inoculated leaf discs were cultured at 20 ° C and 60% rh under a light scheme of 24h dark, followed by 12h lighting / 12h dark, and appropriate levels of disease appeared on untreated control leaf segments At the time of injury (6-8 days after administration), the compound's activity was evaluated as a percentage of disease control when compared to untreated.

Compounds Ie2, Ie3, If3, Ii3, Im3, In3, Iq at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Ir2, Ir3, Is3, Iw2, Iw3, Iy1, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ah.2, Ie43, Is43, Iz43, I.aa.43, I.ao.3, I.ao.43, I.ap.3, I.ap.43 , I.aq.3, I.aq.43, I.ar.3, I.ar.43, I.as.43, I.at.3, I.at.43, I.au.3, I .au.43, I.av.43, I.ax.43, I.ay.3, I.bb.3, I.bb.43, I.be.3 give at least 80% of the disease in this trial control.

Botryotinia fuckeliana ( Botrytis cinerea) / liquid culture (gray mildew )

Fungal conidia from frozen storage were mixed directly into the nutrient broth (Vogels broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), a nutrient culture solution containing fungal spores was added. The test plates were cultured at 24 ° C and the inhibition of growth was determined photometrically 3-4 days after application.

Compounds Ie2, If3, In3, Ir2, Ir3, Iv3, Iw at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 2, Iw3, Iy1, Iy2, I.aa.3, I.ac.3, I.ag.3, I.ah.2, I.ah.3, Is43, I.aa.43, I.au.3, I.ax.3, I.ax.43, I.ay.3 gave at least 80% of disease control in this trial.

Wheat eutrophic bacteria ( Gaeumannomyces graminis ) / liquid culture (cereal erosive disease)

Mycelial fragments from cryopreservation were mixed directly into the nutrient medium (PDB potato dextrose medium). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), a nutrient culture solution containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically 4-5 days after application.

Compounds Ia3, Ib3, Ic3, Id3, Ie2, Ie3, If at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Ig3, Ih3, Ii3, Ij3, Ik3, Im3, In3, Io3, Ip3, Iq3, Ir2, Ir3, Is3, It3, Iu3, Iv3, Iw2, Iw3, Ix3, Iy1, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I. af.3, I.ag.3, I.ah.2, I.ah.3, I.ai.3, I.aj.3, I.ak.3, I.am.3, and I.an. 3 Give at least 80% of disease control in this trial.

Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (anthrax)

The fungal conidia from the cryopreserved material was directly mixed into the nutrient medium (PDB potato glucose medium). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), a nutrient culture solution containing fungal spores was added. The test plates were cultured at 24 ° C and the inhibition of growth was measured photometrically 3 to 4 days after application.

Compounds Ia3, Ib3, Ic3, Ie2, Ie3, If3, Ih at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Ii3, Ik3, Im3, In3, Ip3, Iq3, Ir2, Ir3, Is3, It3, Iu3, Iv3, Iw2, Iw3, Ix3, Iy1 Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ag.3, I.ah.2, I. ah.3, Ie43, Is43, Iz43, I.aa.43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I .aq.43, I.at.3, I.at.43, I.au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I.ax .43, I.ay.3, I.bb.3, I.bb.43, I.be.3, I.bf.3 gave at least 80% of disease control in this trial.

Magnaporthe grisea (Pyricularia oryzae) / rice / leaf disc prevention (Rice Blast)

The rice leaf segment cultivar Cv. Ballila was placed on agar in a multiwell plate (24 well format), sprayed with a test compound formulated with DMSO and Tween20, and diluted in water. After 2 days after application, the leaf fragments were inoculated with a spore suspension of the fungus. The inoculated leaf segments were cultured in a climatic chamber under a light scheme of 24h dark followed by 12h light / 12h dark at 22 ° C and 80% rh, and appropriate levels appeared in untreated control leaf discs At the time of disease damage (5 to 7 days after administration), the compound's activity was evaluated as a percentage of disease control when compared to untreated.

Compounds Ia3, Ib3, Ie3, If3, If3, Ik3, Im3, In at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Ip3, Ir2, Ir3, Is3, It3, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ah.2, Is43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I.ar.43, I.at.3, I.at.43, I. au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I.ax.43, I.ay.3, I.bb.3, I.bb. 43 At least 80% of disease control was given in this trial.

Monographella nivalis (Microdochium nivale) / liquid culture (cereal root rot)

The fungal conidia from the cryopreserved material was directly mixed into the nutrient medium (PDB potato glucose medium). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), a nutrient culture solution containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically 4-5 days after application.

Compounds Ia3, Ib3, Ic3, Id3, Ie2, Ie3, If at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Ii3, Ig3, Ih3, Ik3, Im3, In3, Ip3, Iq3, Ir2, Ir3, Is3, It3, Iu3, Iv3, Iw2, Iw3, Ix3, Iy1, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ag.3, I. ah.2, I.ah.3, I.ai.3, I.aj.3, Ie43, Is43, Iz43, I.aa.43, I.ao.3, I.ao.43, I .ap.3, I.aq.3, I.at.3, I.au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I.ax .43, I.ay.3, I.bb.3, I.bb.43, I.bf.3 gave at least 80% of disease control in this trial.

Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot)

The fungal conidia from cryopreservation were mixed directly into the nutrient medium (PDB potato dextrose medium). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), a nutrient culture solution containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically 4-5 days after application.

Compounds Ib3, Ie2, Ie3, If3, Im3, In3, Ip at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Iq3, Ir2, Ir3, Is3, Iv3, Iw2, Iw3, Ix3, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ae.3, I.ah.3, Is43, Iz43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I. at.3, I.at.43, I.au.3, I.ax.3, I.ax.43, I.bb.3, I.bb.43 Give at least 80% of disease control in this trial .

Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch)

The fungal conidia from the cryopreserved material was directly mixed into the nutrient medium (PDB potato glucose medium). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), a nutrient culture solution containing fungal spores was added. The test plates were cultured at 24 ° C and the inhibition of growth was determined photometrically 4 to 5 days after application.

Compounds Ia3, Ib3, Ic3, Ie2, Ie3, If3, Ih at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Ik3, Im3, In3, Ip3, Iq3, Ir2, Ir3, Is3, It3, Iu3, Iv3, Iw2, Iw3, Ix3, Iy1, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ag.3, I.ah.2, I.ah.3 , I.ak.3, Ie43, Is43, Iz43, I.aa.43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq. 3.I.aq.43, I.ar.43, I.as.43, I.at.3, I.at.43, I.au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I.ax.43, I.bb.3, I.bb.43, I.be.3 gave at least 80% of disease control in this trial.

Wheat Puccinia recondita f.sp. tritici / wheat / leaf disc prevention method (brown rust)

The wheat leaf segment cultivar Cv. Kahzler was placed on agar in a multiwell plate (24-well format) and sprayed with a formulated test compound diluted in water. One day after application, the leaf discs were inoculated with a spore suspension of the fungus. When the inoculated leaf segments were cultured in a climatic chamber under a 12h light / 12h dark light scheme at 19 ° C and 75% rh, and an appropriate level of disease damage appeared in untreated control leaf discs ( 7-9 days after administration), the activity of the compounds was evaluated as a percentage of disease control compared to the untreated.

Compounds Ia3, Ib3, Ic3, Ie2, Ie3, If3, Ii at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.Im3, In3, Ip3, Ir2, Ir3, Is3, It3, Iw2, Iw3, Iy1, Iy2, Iy3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ah.2, Ie43, Is43, Iz43, I.aa.43, I.ao.3, I.ao.43 , I.ap.3, I.ap.43, I.aq.3, I.aq.43, I.ar.43, I.as.43, I.at.3, I.at.43, I .au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I.ax.43, I.ba.43, I.bb.3, I.bb .43, I.bf.3 gave at least 80% of disease control in this trial.

Pyrenophora teres / barley / leaf disc preventative (reticulatae)

The barley leaf segment cultivar Cv. Hasso was placed on agar in a multiwell plate (24 well format), sprayed with a test compound formulated with DMSO and Tween20, and diluted in water. After 2 days after application, the leaf fragments were inoculated with a spore suspension of the fungus. When the inoculated leaf segments were cultured in a climatic chamber under a 12h light / 12h dark light scheme at 20 ° C and 65% rh, and appropriate levels of disease damage appeared in untreated control leaf discs ( 5-7 days after administration), the activity of the compounds was evaluated as a percentage of disease control compared to the untreated one.

Compounds Ib3, Ie2, Ie3, Ih3, Ir2, Ir3, Is at 200 ppm in this formulation compared to untreated control leaf discs showing extensive mycelial growth under the same conditions 3.It3, Iw2, Iw3, Iy1, Iy2, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, Is43, Iz43, I.ao.3, I.ao.43, I.ap.3, I.aq.3, I.at.3, I.au.3, I.ay.3, I.bb.43 And I.be.3 gave at least 80% of disease control in this trial.

Claims (15)

A compound of formula (I), Of which: R ¹ is halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, of which C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy are optionally used by R ⁶ Represents 1 to 3 group substitutions; R ² and R ^{4 are} independently hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or C ₃ -C ₆ cycloalkyl, where C _1- C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl are optionally substituted by 1 to 3 groups represented by R ⁶ ; R ³ is halogen, C ₁ -C ₆ alkyl , C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, wherein C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl are optionally R ⁶ 1 to 3 groups represented; R ⁵ is C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₃ -C ₁₀ cycloalkyl C ₁ -C ₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, aryl, heteroaryl, wherein the heteroaryl system comprises 1, 2, independently selected from nitrogen, oxygen, and sulfur 5- or 6-membered aromatic monocyclic, heterocyclic group of 3 or 4 heteroatoms, wherein the heterocyclic group comprises 1, 2 or 3 heteroatoms of 4 members, independently selected from nitrogen, oxygen and sulfur, 5 or 6-membered monocyclic non-aromatic, heterocyclic C ₁ -C ₂ alkyl group, or a 5-10 nonaromatic Spirally or bicyclic carbon ring system, the bicyclic ring system optionally comprises carbon independently selected from nitrogen, oxygen and sulfur, 4 or 5 heteroatoms, and optionally by C ₁ -C ₂ alkyl extending A linker is bonded to the rest of the molecule; wherein the C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ alkenyl, and C ₂ Any one of the -C ₁₀ alkynyl moiety is optionally substituted with 1 to 4 groups represented by R ⁷ or 1 group represented by R ⁸ ; or wherein the aryl, heteroaryl, and heterocyclic moiety are Any one of them is optionally substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally by 1 or 2 groups represented by R ⁹ and R ¹⁰ 1 group substitution; or wherein the cyclic or spiro carbon bicyclic ring system is optionally substituted by 1 to 3 groups represented by R ⁷ , or the cyclic carbon bicyclic ring system is optionally substituted by C ₃ -C ₆ cycloalkane Substituents to form a spiro ring moiety; R ^{6 is} independently selected from halogen, cyano, hydroxy, C ₁ -C ₆ alkoxy, and C ₃ -C ₆ cycloalkyl; R ^{7 is} independently selected from halogen, cyano , hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl , C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C _1-2 alkyl, C ₂ -C ₆ fluorenyl, C ₂ -C ₆ fluorenyloxy, C ₂ -C ₆ fluorenyloxy C ₁ -C ₆ alkyl and C ₁ -C ₄ alkoxycarbonyl; wherein when R ⁷ is when C _1-2 alkyl group C, the C ₃ -C ₆ cycloalkyl optionally substituted alkyl moieties independently selected from halogen and C ₁ -C ₆ alkyl group having 1 or 2 groups ₃ -C ₆ cycloalkyl R ⁸ is aryl, aryloxy, aryl C ₁ -C ₆ alkyl, heteroaryl, wherein the heteroaryl system comprises 1, 2, 3 or 4 independently selected from nitrogen, oxygen and sulfur 5 or 6 membered aromatic monocyclic, heteroaryloxy or heteroaryl C ₁ -C ₆ alkyl groups, of which aryl and heteroaryl are optionally 1 to 3 represented by R ⁹ Group or 1 group substitution represented by R ¹⁰ ; R ^{9 is} independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkane Alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy, of which C ₁ -C ₆ alkyl, C _1- C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy is optionally substituted by 1 to 3 groups represented by R ¹¹ ; R ^{10 is} selected from C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, aryl C ₁ -C ₆ alkyl, heteroaryl, wherein the heteroaryl system comprises independently selected from nitrogen, oxygen 5- or 6-membered aromatic monocyclic, 1, 2, 3, or 4 heteroatoms with sulfur, heteroaryloxy, heteroarylthio, heteroaryl C ₁ -C ₆ alkyl, heterocyclic Wherein the heterocyclyl system comprises a 4-, 5- or 6-membered non-aromatic monocyclic, heterocyclyloxy, heterocyclyl group of 1, 2 or 3 heteroatoms independently selected from nitrogen, oxygen and sulfur. Thio or heterocyclyl C ₁ -C ₆ alkyl, of which C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryl oxy, arylthio, aryl-C ₁ -C ₆ alkyl, aryl, heteroaryl, heteroaryloxy, heteroarylthio, heteroaryl-C ₁ -C ₆ alkyl, heterocyclyl, heteroaryl Cyclooxy, heterocyclylthio, and heterocyclyl C ₁ -C ₆ alkyl are optionally substituted with 1 to 3 groups represented by R ¹¹ ; R ^{11 is} independently selected from halogen and methyl; X is CH or N; or its salt or N-oxygen Compound.     The compound as described in item 1 of the scope of patent application, wherein X is C-H.     The compound according to item 1 or item 2 of the scope of patent application, wherein R ¹ is halogen, cyano, methyl, trifluoromethyl, methoxy or trifluoromethoxy. The compound according to any one of claims 1 to 3, wherein R ² is hydrogen. The compound according to any one of claims 1 to 4, wherein R ³ is halogen or C ₁ -C ₄ alkyl. The compound according to any one of claims 1 to 5, wherein R ⁴ is hydrogen. The patentable scope of application of the compound according to any 1 to 6, wherein: R ⁵ C ₁ -C ₇ alkyl-based, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ -cycloalkyl C ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, C ₂ -C ₇ alkynyl, phenyl, heteroaryl, wherein the heteroaryl system comprises independently selected from nitrogen 5 or 6 membered aromatic monocyclic, heterocyclic groups of 1, 2, 3 or 4 heteroatoms of oxygen, oxygen and sulfur, wherein the heterocyclic group comprises 1, 2 independently selected from nitrogen, oxygen and sulfur 4-membered, 5-membered or 6-membered non-aromatic monocyclic or heterocyclic C ₁ -C ₂ alkyl or 5-membered to 10-membered non-aromatic cyclic or spiro carbon bicyclic ring system with 3 heteroatoms, the carbon The bicyclic system optionally contains 1, 2, or 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and is optionally bonded to the remainder of the molecule through a C ₁ -C ₂ alkyl linker; wherein Any of the C ₁ -C ₇ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, and C ₂ -C ₇ alkynyl moieties are optionally R ⁷ 1 to 4 groups represented or 1 group substituted by R ⁸ ; or wherein any of the phenyl, heteroaryl, and heterocyclyl moieties Optionally substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ or optionally by 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ Group substitution; or wherein the cyclic or spiro carbon bicyclic ring is optionally substituted with 1 to 3 groups represented by R ⁷ , or the cyclic carbon bicyclic ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form Spiral ring section. The compound as described in any one of claims 1 to 7, wherein: R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₅ cycloalkyl C _{1 -2} alkyl, C ₂ -C ₆ alkynyl, phenyl, heterocyclic, wherein the heterocyclic group is a 4- or 6-membered non-aromatic monocyclic, heterocyclic C ₁ alkyl group containing one oxygen atom , Or a 5- to 9-membered non-aromatic cyclic or spiro carbon bicyclic ring system, the carbon bicyclic ring system optionally contains 1 oxygen atom, and optionally bonded to the remainder of the molecule through a methylene linker; Any one of the C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, and C ₂ -C ₆ alkynyl moieties is optionally represented by 1 to 4 groups represented by R ⁷ or R ⁸ 1 group substitution; or wherein any one of the phenyl or heterocyclyl moiety is optionally substituted by 1 or 2 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally by 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; or wherein the cyclic or spiro carbon bicyclic ring system is optionally substituted by 1 or 2 groups represented by R ⁷ , Or the cyclic carbon bicyclic ring system is optionally C ₄ -C ₅ cycloalkyl Substitute to form a spiro ring. The compound as described in any one of claims 1 to 8, wherein: R ⁵ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, or C ₃ -C ₆ cycloalkyl C ₁ -C ₂ alkyl, wherein any one of the C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl, and C ₃ -C ₆ cycloalkyl moiety is optionally represented by R ⁷ 1 to 4 groups represented by or 1 group represented by R ⁸ , wherein R ^{7 is} independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C _1-2 alkyl, and C ₁ -C ₃ alkoxycarbonyl, and R ⁸ is optionally a phenyl, benzyl or iso group substituted by 1 to 3 groups represented by R ⁹ or 1 group represented by R ¹⁰ Azole, and wherein R ⁹ is a halogen and R ¹⁰ is a phenyl group optionally substituted with 1 to 3 groups represented by halogen as R ¹¹ ; or R ⁵ is a phenyl group, an oxetanyl group, a tetrahydrofuryl group or tetrahydropyran-yl, each being optionally represented by R ⁹ to 1 3 groups or 1 R & lt radicals represented by ^10, represented by R ⁹ or one or two of the radicals R ¹⁰ and Represented by 1 group substitution, wherein R ^{9 is} independently selected from halogen and C ₁ -C ₄ alkyl, and R ^{10 is} selected from phenyl groups each optionally substituted by 1 to 3 groups represented by R ¹¹ , Benzyl or C ₆ -C ₈ cycloalkoxy; or R ⁵ is a cyclic or spiro ring system selected from: Each is optionally substituted with 1 to 3 groups represented by R ⁷ independently selected from C ₁ -C ₄ alkyl and C ₂ -C ₄ amidinooxy C ₁ -C ₄ alkyl. The compound as described in any one of claims 1 to 9, wherein: R ⁵ is C ₁ substituted by ₁ group optionally represented by R ⁷ selected from C ₃ -C ₆ cycloalkyl -C ₄ alkyl; or R ⁵ is a cyclic or spiro ring system selected from: Each is optionally substituted by 1 to 3 groups represented by R ⁷ independently selected from C ₁ -C ₄ alkyl. The compound as described in claim 10, wherein when R ⁵ is a cyclic or spiro ring system, R ⁷ is a methyl group.     An agricultural chemical composition contains a fungicidal effective amount of the compound of formula (I) as described in any one of claims 1 to 11 of the scope of patent application.         The composition according to item 12 of the application, further comprising at least one additional active ingredient and / or agrochemically acceptable diluent or carrier.         A method for controlling or preventing the infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidal effective amount of a compound of formula (I) as described in any one of claims 1 to 11 of the patent application scope, A composition containing such a compound as an active ingredient is applied to such plants, parts thereof, or a place thereof.         Use of a compound of formula (I) as a fungicide as described in any one of claims 1 to 11 of the scope of patent application.